Symposium On Size Selected Clusters 2007

Contents
Talks Monday - Cluster Physics . . . . . . Tuesday - Clusters and Biomolecules Wednesday - Clusters and Hydrogen Thursday - Cluster Chemistry . . . . Posters - Session A Clusters and Biomolecules Magnetism . . . . . . . . Metal Clusters . . . . . . Methods and Machines . . Molecular Clusters . . . . Phase Transitions . . . . . Rare Gas Clusters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 3 15 29 41
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Posters - Session B Carbon and Silicon . . . . . . . Clusters and Hydrogen . . . . . Deposited Clusters . . . . . . . Dynamics . . . . . . . . . . . . Reacted Clusters and Catalysis
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Index 191 List of Authors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
Talks
Monday - Cluster Physics
TALKS
MONDAY - CLUSTER PHYSICS
Time-resolved ionic caging dynamics

W. Carl Lineberger JILA and Department of Chemistry and Biochemistry University of Colorado, Boulder, Colorado 80309
Ultrafast pump-probe studies of recombination in partially solvated, size-selected dihalide cluster anions show long time coherent motions and the resulting non-statistical energy ow in the cluster. For photodissociated I (CO2 )n , we observe new type of recombination: a solvent asymmetry-driven 2 energy transfer process without a condensed phase counterpart. Very short recombination times are observed (10 ps) with the chromophore only partially solvated, and the time required for recombination steadily decreases with additional solvation. Theoretical models point to the central role of the solvent electric eld in the recombination process, but suggest electron transfer processes that cannot be tested with a homonuclear dihalide chromophore. To further test these concepts, we investigate the time-resolved recombination of photodissociated IBr (CO2 )n clusters following excitation to the dissociative IBr A 2 1/2 state of the chromophore. In complete contrast to previous studies involving solvated I , the observed recombination times for IBr (CO2 )n increase 2 dramatically with increasing cluster size, from 12 ps for n = 5 to 900 ps for n= 8,10. The basis for this dramatic dierence gives increased credence to the utility of a "solvent coordinate" description of geminate recombination.
TALKS
Cage Clusters of Gold and Tin: Golden Buckyballs and Stannaspherene

Lai-Sheng Wang Department of Physics, Washington State University, 2710 University Drive, Richland, WA 99354, USA and Chemical & Materials Science Division, Pacic Northwest National Laboratory, P.O. Box 999, Richland, WA 99352, USA.
Photoelectron spectroscopy (PES) yields direct electronic structure information for size-selected clusters. Combining PES with theoretical calculations has become an eective approach to obtain structural information for small and medium-sized clusters. We present recent discoveries of two classes of cage clusters in gold and tin. Negatively charged gold clusters (Au ) have been shown n to exhibit a remarkable structural diversity from 2D structures for n = 4-12 and the pyramidal structure for n = 20. Using PES and DFT calculations, we have found that gold clusters with n = 16 and 17 possess unprecedented hollow cage structures [1]. We have been able to successfully dope a variety of foreign atoms into the empty spaces in the golden cages, conrming their structural robustness, as well as demonstrating chemical tuning of their electronic, magnetic, and catalytic properties [2]. Unlike carbon, the heavier congeners of the group 14 elements are not known to form hollow cage structures similar to the fullerenes. In a recent PES study of tin clusters [3], we noted that the spectrum of Sn is distinctly dierent from that of its neighbors or its Si/Ge counterpart. This 12 observation led to our discovery of a highly symmetric and stable icosahedral Sn2 cage [4], for 12 which we coined a name "stannaspherene" to describe its high symmetry and spherical p bonding. We have also shown that all transition metals including the f-block elements can be doped inside Sn2 to form a whole class of endohedral stannaspherenes [5], which may be used as potential 12 building blocks for new cluster-assembled materials.
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Figure 1: (a) Au 16
(b) Cu@Au 16
(c) Sn2 12
(d) M @Sn12
[1]"Evidence of Hollow Golden Cages" (S. Bulusu, X. Li, L. S. Wang, and X. C. Zeng), Proc. Natl. Acad. Sci. (USA) 103, 8326-8330 (2006). [2]"Doping the Golden Buckyballs: Cu@Au and Cu@Au " (L. M. Wang, S. Bulusu, H. J. Zhai, X. C. Zeng, and 16 17 L. S. Wang), Angew. Chem. Int. Ed., in press (2007). [3]"Evolution of the Electronic Properties of Snn - Clusters (n = 4 - 45) and the Semiconductor-to-Metal Transition" (L. F. Cui, L. M. Wang, and L. S. Wang), J. Chem. Phys. 126, 064505-1-8 (2007). [4]"Sn122 -: Stannaspherene" (L. F. Cui, X. Huang, L. M. Wang, D. Y. Zubarev, A. I. Boldyrev, J. Li, and L. S. Wang), J. Am. Chem. Soc. 128, 8390-8391 (2006). [5]"Endohedral Stannaspherenes (M@Sn ): A Rich Class of Stable Molecular Cage Clusters" (L. F. Cui, X. Huang, 12 L. M. Wang, J. Li, and L. S. Wang), Angew. Chem. Int. Ed. 46, 742-745 (2007).
TALKS
Transport Properties through Molecular Clusters by First-principles Calculations

Hiroshi Mizuseki1 , Rodion V. Belosludov1 , Amir A. Farajian1,2 , Tomoki Uehara1 , and Yoshiyuki Kawazoe1 1. Institute for Materials Research, Tohoku University, Sendai, 980-8577, Japan 2. Center for Nanoscale Science and Technology, Department of Mechanical Engineering and Materials Science, Rice University, Houston, USA
Molecular devices are potential candidates for this next step, and they would make it possible to realize the most advantageous devices. However, source of expenditure is necessary that such a large number of organic molecules can be obtained by synthetic chemistry, so any means of exploring their properties and behavior in order to predict the relevant properties of a molecule in advance of its synthesis would be extremely useful. Our group has covered a wide range of molecular clusters [1] which have potential application in molecular devices using rst-principles calculations and nonequilibrium Greens function formalism. There are supramolecular wires [2], porphyrin [3], [4] and ferrocene [5] molecules and so on. In this presentation, we will present our recent study on the transport properties of a ferrocene-based molecule wire using the nonequilibrium Greens function formalism for quantum transport and the density functional theory (DFT) of electronic structures using local orbital basis sets. The ferrocene has high degree of chemical and thermal stability in dierent environments and a wealth of synthetic methods for the construction of a variety of relatively complex ferrocene-based systems. Molecular wires based on ferrocene molecules are compact and linear, which may allow one to incorporate such wires into bulky molecules to create a shielded molecular wire. Iron substitution by dierent metals will also aect electron transport through the cyclopentadienyl ring. First, the transport properties of two ferrocenedithiolate systems with dierent ve-member ring connections have been estimated and the results of the calculations reveal that the iron atom enhances the conductivity of the ferrocene molecule compared with all-organic molecules. Moreover, the conductance through the ferrocene molecule depends on the position of sulfur atoms. The molecule has a higher electrical conductivity at low bias when the same cyclopentadienyl ring is connected to an gold electrode by sulfur atoms. The I-V characteristics show that, in this case the transport properties of the molecule have metallic features. The transmission coecients of ferrocenedithiolate molecules changed with applied bias. This is attributable to the shift of energy levels and the change of molecular orbital shape by the electric eld. The several structures of molecular wire based on ferrocene molecules have been proposed and their transport properties have been also estimated and analyzed.
[1]http://www-lab.imr.edu/ mizuseki/nanowire.html [2]R. V. Belosludov, A. A. Farajian, H. Mizuseki, K. Ichinoseki, and Y. Kawazoe, Jpn. J. Appl. Phys., 43, 2061 (2004). [3]R. V. Belosludov, A. A. Farajian, H. Baba, H. Mizuseki, and Y. Kawazoe, Jpn. J. Appl. Phys., 44, 2823 (2005). [4]A. A. Farajian, R. V. Belosludov, H. Mizuseki, and Y. Kawazoe, Thin Solid Films, 499, 269 (2006). [5]T. Uehara, R. V. Belosludov, A. A. Farajian, H. Mizuseki, and Y. Kawazoe, Jpn. J. Appl. Phys., 45, 3768 (2006).
TALKS
Density functional modeling of free and supported clusters: on the road to an understanding of nanoscale catalysis
Michael Moseler Fraunhofer Institute for Mechanics of Materials IWM, Whlerstr. 11, 79108 Freiburg, Germany Freiburg Materials Research Center, Stefan-Meier-Str. 21, 79104 Freiburg, Germany
Understanding and predicting heterogeneous catalysis remains one of the main motivations underlying the science of gasphase and supported nano-cluster. Gasphase and surface science experiments already provide important contributions to our knowledge how nano-particles catalyse reactions [1]. Often however, this progress is only achieved in combination with quantum-chemical atomistic simulations. Here we show how density functional theory can be used to understand experimental size evolutionary patterns in the activity of gasphase and metal oxide supported Pd clusters [2], [3]. We provide theoretical as well as experimental evidence that the reaction of supported PdN with molecular oxygen results in the formation of nano-oxides which are in epitaxy with the ceramic support. These oxide serve as a Mars-van-Krevelen oxygen reservoir and therefore play an important role in the catalyzed combustion of carbon monoxide. The calculated low-temperature pathways for the oxide-formation and the CO oxidation are in perfect agreement with the experimentally observed reaction conditions. The theoretical explanation of the observed reactivity of gold cluster anion towards adsorption of molecular oxygen [4] provides a second example for the successful application of density functional theory to elucidate catalytic mechanisms [5]. Experimentally an odd-even oscillation in the O2 take-up of Au clusters is observed (a pattern which can be easily explained by open spin shells). n We found an explanation for anomalies in this odd-even pattern occurring e.g. for Au . The 16 reactive cluster states belong to a partial jellium model of the gold 6s electrons. In this model the hexadecamer anion is close to a shell closing and therefore behaves halogen-like. Consequently, electron donation to the oxygen dimer is strongly reduced resulting in the inertness of the cluster.
Figure 1: Majority-spin Kohn-Sham energies of the Au and Au cages and the Au tetrahedron. 16 18 20 The length of the energy-level bars represents the added weight of the atomic s and p orbitals forming the wavefunctions. Blue bars denote high s+p weights; red bars represent states that are mostly formed by atomic d orbitals (the "d band"). The majority-spin Fermi energy is depicted in green. Isosurfaces of representative jelliumlike orbitals of Au are displayed on the right-hand side along 20 with a classication into jellium-type states. Also included is an isosurface of a d state (in green and red) illustrating localization about the atomic centers that form the tetrahedral skeleton of the Au cluster. 20
[1]U. Heiz, E. L. Bullock, Mater. Chem. 14, 564 (2004). [2]B. Huber, P. Koskinen, H. Hkkinen and M. Moseler, Nature Materials 5, 44 (2006) [3]B. Huber, H. Hkkinen, U. Landman and M. Moseler, Comp. Mat. Sci. 35, 371 (2006) [4]Y. D. Kim, M. Fischer, G. Gantefr, Chem. Phys. Lett. 377, 170 (2003) [5]B. Yoon, P. Koskinen, B.H uber, O. Kostko, B. von Issendor, H. Hkkinen, M.M oseler and U. Landman, Chem.Phys.Chem. 8, 157 (2007)
TALKS
Angle-resolved photoelectron spectroscopy of cold Na cluster anions

Christof Bartels, Christian Hock, Jan Huwer and Bernd v.Issendor Fakultt fr Mathematik und Physik, Universitt Freiburg, Stefan-Meier-Strae 19, 79104 Freiburg, Germany
Angle and energy-resolved photoelectron spectroscopy has been performed on cold (20 K) sizeselected Na cluster anions in a wide size range using ns laser pulses with wavelengths from UV to IR. For the smallest clusters (2, 3, 4, 5, 7 atoms), the occupied molecular orbitals can be described as linear combinations of the atomic valence orbitals. The observed transitions can be assigned to these molecular orbitals, and the evolution of the emission patterns with laser wavelength is in qualitative agreement with what one expects from the symmetry of the orbitals. Bigger Na clusters, which have been investigated earlier by energy-resolved photoelectron spectroscopy [1], can be described in the framework of the jellium model. This model neglects the ionic background and treats the clusters valence electrons as free electrons in eective single-particle potentials, leading to an electronic shell structure similar to the well-known atomic shells, assigning energy and angular momentum quantum numbers to the most loosely bound electrons of the cluster. For single-photon excitation with linearly polarized light, the angular distribution of photoelectrons can be described by a single anisotropy parameter. This parameter has been calculated for Na clusters using simple Woods-Saxon potentials; it shows variations with wavelength, which are characteristic for the dierent angular momentum eigenstates. We have measured the evolution of this asymmetry parameter in the wavelength range 290. . . 755 nm for selected cluster sizes (19, 21, 33, 34, 55, 147). The experimental results will be presented and compared to our calculations.
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Figure 1: Experimental images of photoelectrons (rst row) and the corresponding electron velocity distributions (second row) for Na at wavelengths 308, 348, 460 and 650 nm (from left to right). 3 The electron velocity distributions were reconstructed using the pBasex program [2].
[1]G. Wrigge, M. Astruc Homann and B. v.Issendor, Phys. Rev. A 65, 063201 (2002). [2]G. A. Garcia, L. Nahon and I. Powis, Rev. Sci. Instr. 75 (11), 4989 (2004).
TALKS
Where does the giant response in spin-dependent transport measurements of magnetic clusters in metallic matrices come from?
G. Di Domenicantonio, M. Hillenkamp, C. Flix EPFL, Lausanne, Switzerland
We have observed giant responses of up to several hundred percent in spin-dependent transport measurements of samples with well-dened Cobalt clusters embedded in Copper and Silver matrices [1]-[3]. These magnetic eld dependencies are notably pronounced for smallest clusters of a few atoms only. An analysis in terms of spin disorder scattering reects our observations on a qualitative level and yields a mean magnetic moment per cluster. While not yet performed with truly mass-selected clusters, we demonstrate the feasibility of the method with narrow size distributions between single atom and several thousands. The possibility to derive information on size-dependent magnetic moments, the interaction between conduction electron spin and localized magnetic moment and dynamic eects like elastic spin mixing are discussed.
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Figure 1: Magneto-thermogalvanic voltage (MTGV) and GMR for Co clusters in Ag.

[1]S. Serrano-Guisan, G. Di Domenicantonio, M. Abid, J.-P. Abid, M. Hillenkamp, L. Gravier, J.-P. Ansermet and C. Flix, Nature Materials 5, 730 (2006) [2]M. Hillenkamp, G. Di Domenicantonio, C. Flix, L. Gravier, S. Serrano-Guisan and J.-P. Ansermet, accepted for Eur. Phys. J. B, (2007) [3]L. Gravier, S. Serrano-Guisan, G. Di Domenicantonio, M. Abid, M. Hillenkamp, C. Flix and J.-P. Ansermet, Europhys. Lett., 77, 17002 (2007)
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TALKS
Room-Temperature Isolation of Organometallic Functional Sandwiches via Soft-Landing into n-Alkanethiol Self-Assembled Monolayers
Atsushi Nakajima Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan CREST, Japan Science and Technology Agency (JST), c/o Department of Chemistry, Keio University, Yokohama 223-8522, Japan
The adsorption state and thermal stability of organometallic sandwich clusters of vanadium (V) - benzene (Bz), V(Bz)2 and V2 (Bz)3 , soft-landed onto a self-assembled monolayer of dierent chain-length n-alkanethiols (Cn -SAM, n = 8, 12, 16, 18, and 22) were studied by means of infrared reection absorption spectroscopy (IRAS) and temperature programmed desorption (TPD). The IRAS measurement conrmed that V(Bz)2 clusters are molecularly adsorbed and maintain a sandwich structure on all of the SAM substrates. In addition, the clusters supported on the SAM substrates are oriented with their molecular axes tilted 70-80 o the surface normal. An Arrhenius analysis of the TPD spectra reveals that the activation energy for the desorption of the supported clusters increases linearly with the chain-length of the SAMs. For the longest chain C22 -SAM, the activation energy reaches 150 kJ/mol, and the thermal desorption of the supported clusters can be considerably suppressed near room temperature. The clear chain-length-dependent thermal stability of the supported clusters observed here can be explained well in terms of the cluster penetration into the SAM matrixes. Besides, the vibrational assignment of the IRAS spectrum for the V2 (Bz)3 sandwich was based on a harmonic frequency analysis that employed density functional theory. The close similarity between the experimental and calculated results for the IR absorption frequencies demonstrates that the V2 (Bz)3 complexes have a multidecker sandwich structure on the SAM substrate. Our thermal desorption study established that the sandwich complexes can be isolated on the SAM substrate up to a high temperature of 350 K.
[1]S. Nagaoka, T. Matsumoto, K. Ikemoto, M. Mitsui, A.Nakajima, "Soft-landing isolation of multidecker V2 (Bz)3 complexes in an organic monolayer matrix: an infrared spectroscopy and thermal desorption study," J. Am. Chem. Soc. 129, 1528 (2007). [2]S. Nagaoka, T. Matsumoto, E. Okada, M. Mitsui, A.Nakajima, "Room-temperature isolation of V(Bz)2 sandwich clusters via soft-landing into n-alkanethiol self-assembled monolayers," J. Phys. Chem. B 110, 16008 (2006). [3]M. Mitsui, S. Nagaoka, T. Matsumoto, A. Nakajima, "Soft-landing isolation of vanadium- benzene sandwich clusters on a room-temperature substrate using n-alkanethiolate self-assembled monolayer matrices," J. Phys. Chem. B (Letter) 110, 2968 (2006). [4]K. Miyajima, A. Nakajima, S. Yabushita, M. B. Knickelbein, K. Kaya "Ferromagnetism in one-dimensional vanadium-benzene sandwich clusters," J. Am. Chem. Soc. 126, 13202 (2004).
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TALKS
Magic Clusters from Gold & Sulphur: Special Stability of Selected Au-Cluster Thiolates, from Orange-Au25 to the SAM Phases
Robert L. Whetten Georgia Institute of Technology - Atlanta, USA
The gold-thiolate system is probably, after carbon, the most widely investigated and exploited class of cluster-assembled materials, oering also, through alloying & plating, an enhanced control of diverse nano-metallic systems. Special ultra-stable i.e. magic compositions, or phases, have been successively identied and isolated. But what is the fundamental basis for their remarkable stability & utility? This question has proven to be surprisingly refractory to analysis, even though the ultimate answers now appear quite simple. In retrospect, one problem was that the nature of the corresponding self-assembled monolayer (SAM) surface phases was profoundly misunderstood. Another problem was that the structural richness of the relevant naked gold clusters was profoundly underestimated. Finally, the mysterious aurophilic interaction between non-bonded gold atoms oers an obscure source of interfacial order & stability. The resulting tragicomedy of errors oers both entertainment & enlightenment.
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TALKS
From Designer Clusters to Synthetic Cluster Assemblies

S. N. Khanna1 and A. W. Castleman, Jr.2 1.Department of Physics, Virginia Commonwealth University, Richmond, VA 23284, USA. 2.Department of Physics and Chemistry, Pennsylvania State University, PA 16802, U.S.A. snkhanna@vcu.edu
One of most promising developments in the eld of clusters and nanoscience is the possibility of synthesizing nanoscale materials where size specic clusters serve as the elementary molecular building blocks. As the physical, chemical, electronic, and magnetic properties of clusters can be tuned by size and composition, this may provide an unprecedented ability to design customized materials. The cluster materials, in addition, possess intra-cluster and inter-cluster length scales leading to novel functionalities not available in conventional materials. While this thought has existed for more than two decades, its realization has been delayed by the reality that clusters are usually metastable and coalesce when assembled. Indeed, the only working example is the alkali-doped-fullerides where fullerenes marked by directional C-C bonds serve as the primary unit. Extending the fullerene experience to other metal and semiconducting systems is likely to emerge as an important frontier in the nanoscience. The talk will focus on our eorts in this direction. I will rst talk about the possibility of forming cluster motifs, based on metals that are fairly stable and maintain their identity upon further growth. These can be classied as superatoms forming a new dimension to the periodic table [1]-[3]. I will then present a new protocol that combines gas phase investigations to examine feasible units, theoretical investigations of energy landscapes and geometrical shapes of feasible units to identify potential motifs, and synthetic chemical approaches to identify and structurally characterize such cluster assemblies in the solid state. Through this approach we have established selected arsenicalkali cluster as a potential building block via gas phase molecular beam experiments. Employing the idea that the particular species identied in the gas phase is a uniquely stable Zintl entity that could eect self-assembly, we report success in synthesizing and characterizing a lattice of analogous super-cluster assembled material. We demonstrate how the electronic properties of such assemblies can be ne tuned.
[1]D. E. Bergeron, A.W. Castleman, Jr., T. Morisato, and S.N. Khanna, Science 304, 84 (2004). [2]D. E. Bergeron, P. J. Roach, A. W. Castleman, Jr., N. O. Jones, and S. N. Khanna, Science 307, 231 (2005). [3]J. U. Reveles, S. N. Khanna, P. J. Roach, and A. W. Castleman, Jr., Proc. Nat. Acad. Sci. 103, 18405 (2006).
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TALKS
Evolution of magnetism in elemental clusters of transition metals

Murilo L. Tiago University of Texas at Austin, USA
Clusters of ferromagnetic atoms (iron, cobalt, nickel) with a few nanometers in size are superparamagnetic: their magnetic moment is unusually high compared to macroscopic samples. One reason for this behavior is the absence of grain boundaries. Another reason is a decrease in delocalization of the "3d" atomic orbitals. Both mechanisms are typical of conned quantum systems. Direct measurements have indicated a strong dependence of magnetic moment with the size of the cluster, especially in iron clusters. In this talk, I will discuss why the size and shape of a cluster aect its magnetic properties. This analysis is based on rst-principles density functional theory. Numerical calculations were done in iron clusters containing up to 400 atoms.
14
Tuesday - Clusters and Biomolecules
TALKS
TUESDAY - CLUSTERS AND BIOMOLECULES
Size-Selected Carbon Cluster Materials

Daniel Ler, Artur Bttcher, Stefan-Sven Jester, Patrick Weis, Sergei Lebedkin and Manfred M. Kappes Institute of Physical Chemistry, University of Karlsruhe and Institute of Nanotechnology, Research Center Karlsruhe, Germany
Ion beam soft-landing has been used to generate multilayer lms of size selected carbon clusters (Cx ; x=50, 52, 54, 56, 58 and 60). We have studied their properties using a range of surface analytical methods including AFM, UPS, XPS, TDS and surface-enhanced Raman spectroscopy. Whereas deposition of C+ generates the well-known v.d.Waals bound molecular solid, smaller fullerenes give 60 rise to covalently linked networks. Interestingly, the major fraction of this deposited network material can be intactly desorbed at elevated temperatures. Experiments probing for dissipation of incident kinetic energy and subsequent surface diusion processes using periodically (pre-)nanostructured pinning sites will also be discussed. These novel materials react with thermal energy atomic hydrogen to make desorbable hydrofullerides [1]-[4].
[1]A. Bttcher, P. Weis, A. Bihlmeier and M. Kappes, Phys. Chem. Chem. Phys. 6, 5213 (2004). [2]A. Bttcher, P. Weis, S. Jester, D. Ler, A. Bihlmeier, W. Klopper and M. Kappes, Phys. Chem. Chem. Phys. 7, 2816 (2005). [3]D. Ler, S. Jester, P. Weis, A. Bttcher and M. Kappes, J. Chem. Phys. 124, 054705 (2006). [4]D. Ler, S. Jester, P. Weis, A. Bttcher and M. Kappes, J. Chem. Phys. 125, 224705 (2006).
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TALKS
Carbon Clusters
Robert N. Compton Department of Physics and of Chemistry, University of Tennessee, Knoxville, TN 37996, USA
Carbon represents the sixth most abundant element in the universe and is the "stu of life", as we know it. Carbon can bond with itself through single, double and triple bonds and, as a consequence, possesses three known allotropes (graphite, diamond and fullerenes). Carbon clusters can exist as linear, branched or cyclic chains, graphene sheets, or fullerenes (including single or multi-walled carbon nanotubes). This talk will attempt to summarize some of the important properties of carbon clusters and their potential applications in technology and medicine. In addition, the recent concerns of the adverse environmental impacts of aqueous colloidal suspensions of so-called nanoC60 , (or n-C60 ) will be briey discussed. Fullerene molecules have unique negative ion properties, exhibiting a large electron attachment cross section from 0 to 20 eV. A second electron can also be bound into a long-lived metastable (C2 , 60 negative electron anity) or stable (C2 , positive electron anity) state which is physically trapped 84 by a Coulomb Barrier. Likewise, low intensity CW laser light can result in ecient ionization of fullerenes through a thermionic emission process[1]. This ease of excitation/ionization makes possible for ecient means of detecting fullerenes as well as their therapeutic use for the thermal destruction of cancer cells. Fullerenes were accidentally discovered by Kroto, Curl and Smalley while sifting through the debris of laser ablated graphite soot looking for carbon clusters which might prove responsible for the socalled Diuse Interstellar Bands (DIBs). The discovery of fullerenes provided some initial excitement that the DIBs might be attributed to the presence of fullerenes or fullerene ions, but this excitement has waned. In another possibility, Prof. P. Sarre has suggested[2] that photo-absorption transitions from valence-bound to dipole-bound anions of interstellar molecules such as CH2 CN might carry the signature of the illusive DIBs. Recently[3], the rst anion (C6 H ) in interstellar space has been identied using microwave spectroscopy. Such a valence bound anion will most certainly possess a dipole-bound state and this ion or others like it (Cn H ) are possible candidates for the DIBs features although the transitions are expected to be somewhat higher in energy. Some carbon clusters may possess quadrupole-bound anions states. In this connection, the possibility that the DIBs may be due to transitions from valence to quadrupole bound anion states of carbon clusters will be considered.
[1]D. Ding et al., Phys. Rev. Lett. 73, 1084(1994). [2]P.J. Sarre, Monthly Notices of the Royal Astronomical Society 313, L14(2000). [3]M. C. McCarthy et al., The Astrophysical Journal, 652, L141(2006).
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TALKS
A novel nanocalorimeter device for free clusters

Fabien Chirot, Sbastien Zamith, Pierre Labastie, Jean-Marc LHermite Laboratoire Collisions, Agrgats, Ractivit (UMR 5589, CNRS - Universit Paul Sabatier), IRSAMC, 31062 Toulouse Cedex 9, France
Thermodynamics of small clusters has received a renewed interest since the pioneering work of Haberland et al [1] who experimentally demonstrated that very small clusters could undergo a phase transition, by measuring caloric curves. Doing calorimetry (in any system) requires to be able to measure the variation of internal energy E corresponding to a variation of temperature T. One possibility is to control the temperature by a heat bath and to read a physical observable, say S, in one to one correspondance with the internal energy. The exact correspondance is not relevant, since we only want to be able to measure when 2 processes end up in the same internal energy. Actually, a known temperature shift T is compensated by a known energy shift E in order to observe the same signal S, and then deduce the heat capacity E/T. In free clusters, the energy is brought either by a laser [1] or by collisions [2] and S is always somehow linked to the evaporation rate, which is very sensitive to the internal energy. A third method measures the mobility of clusters in a drift tube, from which collision cross sections are deduced. The phase transition from liquid to solid is identied thanks to a variation in the cross section [3]. The full caloric curve cannot be obtained in this way however. We propose here a novel method based on an original experimental setup [4] to measure the caloric curve of clusters. The basic idea is to bring energy to the cluster by sticking atoms. After each sticking, the internal energy of the cluster Mn is increased by a known energy. After a given number of sticking collisions nmax the cluster is so heated that it dissociates before it can stick again. nmax is related to the dissociation time, thus is a measure of the internal energy. As in the rst two experiments mentioned above, we can construct the caloric curve by varying T. Our method does not require laser excitation, is easily transferable to many systems and it is model free. We shall present our rst experimental results obtained with sodium clusters. They conrm those of Haberland et al and extend them towards small sizes.
Figure 1: Molecular hydrogen adsorption curve on pure and Li-doped graphene layers.
[1]H. Haberland et al, Phys. Rev. Lett. 94, 035701 (2005). [2]G. A. Breaux et al, Phys. Rev. Lett. 91, 215508 (2003). [3]G. A. Breaux et al, J. Phys. Chem. B, 109, 16575 (2005). [4]F. Chirot et al, Rev. Sci. Instrum. 77, 063108 (2006).
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Photoelectron spectroscopy on mass-selected neutral silver clusters in helium nanodroplets

Josef Tiggesbumker, Andreas Przystawik, Sebastian Gde, Karl-Heinz Meiwes-Broer Institut fr Physik, Universitt Rostock, Universittsplatz 3, 18051 Rostock, Germany
Experiments on mass-selected neutral clusters are often hampered by the broad size distribution delivered by common particle sources. Therefore most of the work concerning the properties of clusters is performed with charged species; in particular most of the work on photoemission has been performed using anionic clusters. We present a method which exploits absorption resonances in order to select a certain cluster size for excitation and ionization from the neutral beam. Atomic Clusters are formed by using the helium nanodroplet pick-up technique. The resulting molecular beam consists of neutral metal clusters embedded in ultracold and superuid droplets. An advantage of helium pickup sources is to almost exclusively prepare clusters in high spin states as already demonstrated with alkali clusters on the surface of droplets [1]. Despite the lack of selectivity in favor of high spin states when growing the clusters inside the droplet we can clearly detect signals from triplet silver dimers [2]. Photoelectron spectra of certain silver clusters are recorded using resonant two-photon excitation for size-selection and ionization. We derive informations on the electronic structure of metal clusters as well as the interaction with the helium environment. An analysis of the spectra recorded at dierent wavelengths shows that in the transition state all investigated systems undergo a rapid relaxation on a picosecond timescale to the lower edge of the absorption band, see the schematic view in Fig. 1. The use of a two-color pump-probe scheme enables for a measurement of the excited state lifetime of the neutral clusters.
Figure 1: Schematic diagram of the ionization dynamics of Ag8 [3] . After excitation to the unoccupied band E roughly 4.0 eV above the ground state, the cluster quickly relaxes to the lower edge EL . In a resonant 2-photon ionization experiment, ionization occurs from this long-living level.
[1]P. Claas, D. Schumacher, F. Stienkemeier, Phys. Rev. Lett. 92, 013401 (2004). [2]A. Przystawik, P. Radclie, S. Gde, K.-H. Meiwes-Broer, J. Tiggesbumker, J. Phys. B 39, S1183 (2006) [3]P. Radclie, A. Przystawik, Th. Diederich, T. Dppner, J. Tiggesbumker, K.-H. Meiwes-Broer, Phys. Rev. Lett. 92, 173403 (2004).
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Unexpected Stability of Al4 H6 : A Borane Analog?

Xiang Li1 , A. Grubisic1 , S. T. Stokes1 , J. Cordes2 , G. F. Gantefr2 , K. H. Bowen1 , B. Kiran3 , M. Willis3 , P. Jena3 , R. Burgert4 and H. Schnckel4 1. Depts. of Chemistry and Materials Science, Johns Hopkins University, Baltimore, MD 21218, USA 2. Dept. of Physics, University of Konstanz, 78457 Konstanz, Germany 3. Department of Physics, Virginia Commonwealth University, Richmond, VA 23284, USA 4. Institute of Inorganic Chemistry, University of Karlsruhe (TH), 76128 Karlsruhe, Germany
While boron has many hydrides, aluminum has been thought to exhibit relatively few. Anion photoelectron spectroscopy and density functional theory were employed to study aluminum hydride clusters, Aln H (4 n 8, 0 m 10). Photoelectron spectra revealed that Al4 H4 , Al4 H6 and a m family of species with general formula Aln Hn+2 (5 n 8) have small adiabatic electron anities and large HOMO-LUMO gaps (ranging from 0.5 to 1.9 eV) relative to those of their stoichiometric neighbors, implying their enhanced stability. Al4 H6 takes on a distorted tetrahedral (D2d ) structure with two counter-positioned bridging hydrogen atoms and shows the largest HOMO-LUMO gap (1.9 eV) of all studied alanes. (Supported by AFOSR)
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Cavity ring-down spectroscopy of gold clusters on surfaces: From the atom to the bulk.
S. Gilb1 , J. Peter1 , A. Kartouzian1 , J.-M. Antonietti1 , K. Hartl1 , M. Michalski1 , U. Heiz1 , A. Del Vitto2 , G. Pacchioni2 , K.H. Lim3 , N. Rsch, H. Jones4 1. Department Chemie, Physikalische Chemie I, Technische Universitt Mnchen, Germany 2. Dipartimento di Scienza dei Materiali, Universit di Milano-Bicocca, Italy 3. Department Chemie, Theoretische Chemie, Technische Universitt Mnchen, Germany 4. Abteilung Laseranwendungen in der Chemie, Universitt Ulm, Germany
Cavity ringdown spectroscopy is a highly sensitive photoabsorption technique which in the last decade has been employed to perform trace detection of molecules or to study weak electronic transitions in both the gas phase and in the liquid phase. We apply this technique in the solid phase in order to measure the absorption of gold nanoparticles on amorphous silica at low coverages. In particular, we explore the evolution of the optical properties of gold in the visible range going from single atoms up to bulk materials. Monodispersed samples of Aun=1,2,4,8,20 where prepared by cluster deposition. Comparison of the gold monomer and dimer spectra demonstrates that soft landing conditions are fullled. Molecularlike optical transitions can be identied up to the tetramer, while larger clusters and particles show characteristic surface plasmon peaks. In addition, the optical properties of the small cluster (n=1,2,4,8) are compared to time dependent TD-DFT calculation. Optically allowed electronic transitions were calculated, and comparisons with the experimental spectra show that silicon dangling bonds [Si], nonbridging oxygen [Si-O], and the silanolate group [Si-O-] act as trapping centers for the gold particles.[1],[2] Large gold particles with a diameter from 1.3 nm to 2.9 nm on SiO2 where also fabricated by the reversed micelle method [3], the samples were measured in air. The measured extinction spectra can be well described by the Mie-Drude model of absorption for small particles.
[1]Del Vitto, A.; Pacchioni, G.; Lim, K. H.; Rsch, N.; Antonietti, J. M.; Michalski, M.; Heiz, U.; Jones, H. Journal of Physical Chemistry B 2005, 109, 19876 [2]Antonietti, J. M.; Michalski, M.; Heiz, U.; Jones, H.; Lim, K. H.; Rsch, N.; Del Vitto, A.; Pacchioni, G. Physical Review Letters 2005, 94. [3]Kstle, G.; Boyen, H. G.; Weigl, F.; Lengl, G.; Herzog, T.; Ziemann, P.; Riethmller, S.; Mayer, O.; Hartmann, C.; Spatz, J. P.; Mller, M.; Ozawa, M.; Banhart, F.; Garnier, M. G.; Oelhafen, P. Advanced Functional Materials 2003, 13, 853.
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Spectroscopy of cold, gas-phase biological ions and their clusters with solvent
Thomas R. Rizzo Laboratoire de chimie physique molculaire, Ecole Polytechique Fdrale de Lausanne, Station 6, CH-1015 Lausanne, Switzerland
At physiological pH, most biological molecules exist as closed-shell molecular ions, where the competition between charge solvation by water and by polar groups the molecule itself helps determine the subtle energetic balance that leads to the stabilization of a particular conformation. To understand more fully the interplay of these interactions, we measure both electronic and vibrational spectra of closed-shell biomolecular ions in the gas phase. We then use these results to test directly the predictions of theory. We measure photofragment spectra of biomolecular ions as well as their clusters with solvent in a home-built tandem quadrupole mass spectrometer containing a 22-pole ion trap cooled to less than 10K. The ions of interest are produced in the gas-phase by electrospray, mass-selected in a quadrupole, and then injected into the trap where they are cooled via collisions with cold helium. After irradiating the ions with IR and/or UV laser pulses, the contents of the trap are ejected and sent through an analyzing quadrupole before being detected. Spectra are generated by monitoring the appearance of a particular fragment ion mass as a function of the laser wave number. This talk will focus on UV and IR/UV photofragment spectroscopy of cold, protonated amino acids [1] as well as their clusters with a few solvent molecules [2]. Our results provide important insight into the interplay of charge and solvent in controlling the photophysics of aromatic amino acid chromophores. I will also discuss our rst steps in applying our techniques to larger peptides.
[1]O. V. Boyarkin, S. R. Mercier, A. Kamariotis, T. R. Rizzo, Journal of the American Chemical Society 128, 2816 (2006). [2]S. R. Mercier et al., Journal of the American Chemical Society 128, 16938 (Dec, 2006).
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Infrared spectroscopic characterization of gas-phase clusters and cluster-adsorbate complexes

Gerard Meijer Fritz-Haber-Institut der Max-Planck-Gesellschaft Faradayweg 4-6, D-14195 Berlin, Germany e-mail: meijer@fhi-berlin.mpg.de
One of the important issues in the study of gas-phase clusters and cluster-adsorbate complexes is to develop experimental methods via which the geometric structure of the clusters and the nature of the adsorption-sites can be unambiguously determined. In principle, infrared absorption spectroscopy, i.e. directly probing the bonds that hold the atoms in the cluster together, is ideally suited for this. Vibrational spectroscopy of (mass-selected) gas-phase clusters remains a very challenging research area, however, due to the combination of low number densities attainable in the gas-phase and a lack of commercially available intense and widely tunable infrared light sources. In this presentation I will give an overview of the various experiments that we have performed over the last years to obtain structural information on gas-phase species via infrared spectroscopic methods. For these experiments, the infrared radiation of the Free Electron Laser for Infrared eXperiments (FELIX) at the FOM-Institute "Rijnhuizen" in Nieuwegein (NL) is used as a source. Dierent experimental detection schemes have been developed some of which are uniquely possible with the FEL to obtain the desired vibrational spectroscopic information. The application of these experimental methods to systems that are of relevance in catalysis will be demonstrated and discussed.
[1]G. von Helden, I. Holleman, G.M.H. Knippels, A.F.G. van der Meer, and G. Meijer, Infrared resonance enhanced multiphoton ionization of fullerenes, Phys. Rev. Lett. 79 (1997) 5234 [2]D. van Heijnsbergen, G. von Helden, M.A. Duncan, A.J.A. van Roij, and G. Meijer, Vibrational spectroscopy of gas-phase metal-carbide clusters and nanocrystals, Phys. Rev. Lett. 83 (1999) 4983 [3]G. von Helden, D. van Heijnsbergen, and G. Meijer, Resonant ionization using IR light: A new tool to study the spectroscopy and dynamics of gas-phase molecules and clusters, J. Phys. Chem. A 107 (2003) 1671 [4]A. Fielicke, A. Kirilyuk, Ch. Ratsch, J. Behler, M. Scheer, G. von Helden, and G. Meijer, Structure determination of isolated metal clusters via far-infrared spectroscopy, Phys. Rev. Lett. 93 (2004) 023401 [5]A. Fielicke, G. von Helden, G. Meijer, D.B. Pedersen, B. Simard, and D.M. Rayner, Gold cluster carbonyls: Saturated adsorption of CO on gold cluster cations, vibrational spectroscopy and implications for their structures, J. Am. Chem. Soc. 127 (2005) 8416
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Inelastic electron interaction (ionization/attachment) with biomolecules embedded in superuid helium droplets
S.Deni, F. Zappa, I. Mhr, T.D. Mrk, P. Scheier Institut fr Ionenphysik und Angewandte Physik, Leopold-Franzens-Universitt Innsbruck, Technikerstrasse 25, A-6020 Innsbruck, Austria
The extensive number of spectroscopy studies with doped helium droplets shows impressively the ability of superuid helium droplets to be a perfect matrix for the preparation and study of cold targets and the formation of complex fragile species [1]. In contrast, inelastic electron interaction with doped helium droplets has been a much less studied subject. This is the more surprising as clusters of biomolecules can be formed from the gas phase by embedding successively single biomolecules into a cold droplet. Moreover, it is known since recently that electrons can induce ecient DNA damage. This is important because in cells secondary electrons are produced with high abundance by ionizing radiation. Thus the underlying chemical and physical processes of the inelastic electron interaction with isolated and also solvated biomolecules is of relevance for the investigation of DNA damage by ionizing radiation and moreover, of fundamental interest in physical chemistry. We have recently constructed a helium cluster source which was initially used to study in detail the properties of electron impact ionization of pure helium clusters [2], as well as metastable decays of helium cluster ions produced [3]. Recently we modied our setup by adding a pick up chamber including molecular beam ovens, a pick up cell and external gas inlets which allow the embedment of various molecules in cold superuid helium droplets. The neutral mixed clusters thus produced are ionized in a Nier type electron impact ion source (with an energy range from about 0 to 150 eV) and ensuing cations and anions are mass analyzed by a high resolution two sector eld mass spectrometer. First studies of the pick up process have been performed with DNA nucleobases adenine and thymine both of which are well studied in the gas phase. Several interesting phenomena could be observed, e.g. in contrast to the gas phase situation electron attachment in this environment leads to the production of parent anions for adenine and thymine [4]. Moreover, site selectivity in the electron attachment process recently discovered in our laboratory for isolated nucleobases [5] is preserved in this complex environment and in addition a novel two step reaction scheme has been proposed to explain characteristic dierences in the attachment spectra. These pick-up experiments have been recently extended by embedding other systems into the helium (and neon) droplets (e.g., chloroform, valine and fullerenes) and in some cases even in the additional presence of water molecules. In case of multiply charged neon droplets we found a serious failure of the previously accepted liquid drop model for vdW bound clusters [6]. This work was partially supported by FWF, Wien, the European Commission, Brussels and the Brazilian agency CNPq.
[1]J. P. Toennies, A. F. Vilesov, Angew. Chem. Int. Ed. 43 2622 (2004). [2]S. Deni, M. Stano, A. Stamatovic, P. Scheier, T. D. Mrk, J. Chem. Phys. 124 054320 (2006). [3]S. Feil, K. Gluch, S. Deni, F. Zappa, O. Echt, P. Scheier and T.D. Mrk, Int. J. Mass. Spectr 252 166 (2006). [4]S. Deni, F. Zappa, I. Mhr, J. Lecointre, M. Probst, T. D. Mrk, P. Scheier, Phys. Rev. Lett., 97 043201 (2006). [5]S. Ptasinska et al., Angew.Chem.Int.Ed. 44 6941 and Phys.Rev.Lett. 95 093201 (2005). [6]I. Mhr et al., Phys.Rev.Lett. 98 023401 (2007).
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Photoabsorption and Photofragmentation in Nanoparticle-biomolecule Hybrid Systems

Roland Mitri1 , Jens Petersen1 , Alexander Kulesza1 , Vlasta Bonai-Kouteck1 , Thibault Tabarin2 , Isabelle Compagnon2 , Michel Broyer2 , Philippe Dugourd2 1. Humboldt Universitt zu Berlin, Institut fr Chemie, Brook-Taylor-Strasse 2, 12489 Berlin, Germany 2. Universit Lyon 1; CNRS; LASIM UMR 5579, bt. A. Kastler, 43 Bvd. du 11 novembre 1918, F-69622 Villeurbanne, France.
We present a joint theoretical and experimental study of the size and structure selective optical absorption and dynamical properties of cationic silver cluster-tryptophan (Trp-Ag+ n=2-5,9) hybrid n systems. Our TD-DFT calculations and MD simulations together with experimentally measured fragmentation channels provide insight into the nature of excitations in interacting nanoparticlebiomolecule subunits and allow to identify characteristic spectral features as ngerprints of two dierent classes of structures: charge solvated and zwitterionic. Dierent types of charge transfer such as from -system of tryptophan to silver cluster or from silver cluster to NH3+ group are characteristic for charge solvated and zwitterionic class of structures, respectively. Remarkably, we observe a strong reduction of the photofragmentation yield in Trp-Ag+ in comparison with free 9 Ag+ which may be attributed to energy dissipation by uorescence. Interplay between internal 9 vibrational energy redistribution and radiationless lifetimes will be addressed. Our ndings provide fundamental insight into the structure- and size-dependent mechanism responsible for the enhanced absorption and emission in nanoparticle-biomolecular hybrid systems.
[1]R. Antoine, T. Tabarin, M. Broyer, P. Dugourd, V. Bonacic-Kouteck, R. Mitric, ChemPhysChem 7, 524 (2006). [2]I. Compagnon, T. Tabarin, M. Broyer, P. Dugourd, R. Mitric, J. Petersen, V. Bonacic-Kouteck, J. Chem. Phys.. 125, 164326 (2006).
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Phase Transition in Polypeptides: A Step towards the Understanding of Protein Folding

Alexander V. Yakubovich, Ilia A. Solovyov, Andrey V. Solovyov and Walter Greiner Frankfurt Institute for Advanced Studies, Max-von-Laue str. 1, 60438 Frankfurt am Main, Germany E-mail: ilia@as.uni-frankfurt.de
The phase transitions in nite complex molecular systems, i.e. the transition from a stable 3D molecular structure to a random coil state or vice versa (also known as (un)folding process) occur or can be expected in many dierent complex molecular systems and in nano objects, such as polypeptides, proteins, polymers, DNA, fullerenes, nanotubes.
Figure 1: The characteristic structural change of alanine polypeptide experiencing an -helix random coil phase transition. We suggest a novel ab initio theoretical method [1] for the description of phase transitions in the mentioned molecular systems. In particular, it was demonstrated that in polypeptides (chains of amino acids) one can identify specic, so-called twisting degrees of freedom, responsible for the folding dynamics of the amino acid chain, i.e. for the transition from a random coil state of the chain to its -helix structure (see Fig. 1). The essential domain of the potential energy surface of polypeptides with respect to these twisting degrees of freedom can be calculated and thoroughly analysed on the basis of ab initio methods such as density functional theory (DFT) or Hartree-Fock method. It is shown [1] that this knowledge is sucient for the construction of the partition function of a polypeptide chain and thus for the development of its complete thermodynamic description, which includes calculation of all essential thermodynamic variables and characteristics, e.g. heat capacity, phase transition temperature, free energy etc. The method has been proved to be applicable for the description of the phase transition in polyalanine of dierent length by the comparison of the theory predictions with the results of several independent experiments and with the results of molecular dynamics simulations. This work was supported in part by INTAS (project No 03-51-6170) and by EU through the EXCELL project.
[1]A. Yakubovich, I. Solovyov, A. Solovyov, and W. Greiner, Eur. Phys. J. D (Highlight paper), 40, 363 (2006); Europhys. News, in print (2007).
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Ion Mobility as a Probe for Molecular Structure and Oligomer States in Biological Assemblies
Michael T. Bowers Department of Chemistry and Biochemistry, University of California Santa Barbara, California, USA
A brief description of the Ion Mobility Method will inaugurate the talk followed by several examples of current systems of interest to our group. Peptide and protein systems of interest will be drawn from those responsible for several important neurological diseases. Recent evidence indicates that Alzheimers disease, Parkinsons disease and the prion diseases are caused by the early aggregation states of misfolded peptides and proteins that eventually go on to form amyloid plaques. The focus will be on the Alzheimers peptide, ABeta. The dominant ABeta peptide is the 40 amino acid fragment AB40 (90% in healthy brains) which is only very mildly neurotoxic. Addition of isoleucine and alanine to the C-terminal end of AB40 yields the strongly neurotoxic AB42 (9% in healthy brains). We have examined the distribution and structure of the early oligomer states of these two systems and related alloforms. Major dierences were found and a new paradigm for the etiology of Alzheimers disease will be proposed. If time permits new data on the Parkinsons protein, Alpha synuclein will be presented including results of two important familial mutants of the wild type. A second part of the talk will deal with the formation and stabilization of G-quadraplexes in DNA. These structures are composed of multiple G-quartets connected by single strand DNA loops and are predicted to be formed by self assembly in G-rich DNA regions in the genome. These G-rich strands are ubiquitous with over 350,000 candidate segments in the human genome, mostly in gene rich regions. In addition, several thousand TTAGGG repeats comprise the telomeric capping regions of all chromosomes whose reproduction is a critical element in cell mytosis. The ability to stabilize G-quadraplexes with diering loop regions may well contribute to possible cures for many types of cancers by selectively silencing gene expression. We will use Ion Mobility and high level molecular dynamics simulations to explore possible drug candidates for stabilizing the quadraplex structure.
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Wednesday - Clusters and Hydrogen
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WEDNESDAY - CLUSTERS AND HYDROGEN
Structure and Reactivity of Transition Metal Oxides: From Gas Phase Clusters to Solid Catalysts
Joachim Sauer Institut fr Chemie, Humboldt-Universitt zu Berlin, Unter den Linden 6, 10099 Berlin, Germany
Transition metal oxides in general and vanadium oxides in particular are viable catalysts for the oxidation and oxygenation of hydrocarbons. Density functional theory (DFT) and other quantum chemical methods in concert with experiments are used to answer questions such as: What is the structure of gas phase cluster ions and how do they dier from supported species and bulk materials [1]-[3]? How can IR spectroscopy and photoelectron spectroscopy in combination with DFT calculations be used to identify global minimum structures among many possible isomers? Can gas phase clusters model the reactivity of solid catalysts and to which extent [4],[5]?
[1]J. Sauer and J. Dbler, Dalton Trans., 2004, 19, 3116 [2]K. R. Asmis, G. Santambrogio, M. Brmmer and J. Sauer, Angew. Chem., 2005, 117, 3182; Angew. Chem., Int. Ed., 44, 3122-3125 [3]E. Janssens, G. Santambrogio, M. Brmmer, L. Wste, P. Lievens, J. Sauer, G. Meijer and K. R. Asmis, Phys. Rev. Lett., 2006, 96, 233401 [4]J. Dbler, M. Pritzsche and J. Sauer, J. Am. Chem. Soc., 2005, 127, 10861 [5]S. Feyel, D. Schrder, X. Rozanska, J. Sauer and H. Schwarz, Angew. Chem., Int. Ed., 2006, 45, 4677; Angew. Chem., 118, 4793-4797
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Materials for Hydrogen Storage: What can Clusters do?

P. Jena Physics Department, Virginia Commonwealth University, Richmond, Virginia 23284-2000, USA pjena@vcu.edu
The success of a new hydrogen economy depends on our ability to nd materials that can store hydrogen with large gravimetric and volumetric densities and operate under ambient thermodynamic conditions. Although host materials consisting of light elements such as Li, Be, B, C, Na, Mg, and Al can meet the gravimetric and volumetric density requirements, the kinetics and thermodynamics of hydrogen sorption are not favorable as the bonding of hydrogen in these materials is either strong (covalent or ionic) or very weak (van der Waals). Ways must, therefore, be found to either weaken or strengthen the hydrogen bond strength so that light metal complex hydrides and materials based on carbon can be used as eective hydrogen storage materials. Two possible ways in which this can be accomplished is to change the chemistry of the hydrogen bonding with host elements through the use of catalysts and/or nanostructures. This talk will discuss the progress that has been made in this direction. In particular, I will discuss the role clusters can play in enhancing our understanding of the interaction of hydrogen with nano-particles and how this interaction can be modied by doping with metal atoms. The systems I will deal with include transition metal and Li coated carbon fullerenes, metal doped organic molecules such as Cn Hn (n=4, 5, 8), and metal decorated ethylene and cispolyacetylene. The stability of these clusters as they are assembled to form bulk cluster assembled materials will also be discussed. The talk will highlight the importance of exploring a novel form of hydrogen bonding where hydrogen is bound to the host materials in nearly molecular form with binding energies that lie between the physisorption and chemisorption states. I will illustrate how this molecular chemisorption of hydrogen is ideal for the fast kinetics and desirable thermodynamics of hydrogen. It is hoped that the understanding gained here can be useful in designing better catalysts as well as hosts for hydrogen storage.
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Chemistry of Transient Species in Water Clusters

Martin K. Beyer Institut fr Chemie, Sekr. C4, Technische Universitt Berlin, Strae des 17. Juni 135, 10623 Berlin, Germany
Reactions of ionic water clusters - or hydrated ions - in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer, proceed analogous to solution phase reactions [1],[2]. This idea is applied to study aqueous chemistry of species which are short-lived in aqueous solution. Examples of such transient species are the hydrated electron[3] and monovalent transition metal ions [4]. In the gas phase experiment, individual reaction steps are identied unambiguously, since the nature of the reactive species is dened, in contrast to bulk solutions. Recent results suggest that also thermochemical information can be directly inferred from the experiment via the quantitative analysis of the number of evaporating water molecules. This approach is exemplied with the reactions of carbon dioxide with hydrated electrons (H2 O) . n Monovalent vanadium is metastable in the cluster, and is oxidized to V(II) or V(III) with formation of atomic or molecular hydrogen, respectively [5]. These reactions are strongly size-dependent. Temperature resolved experiments with a nitrogen-cooled ICR cell, controlling the black-body radiation temperature experienced by the clusters between 86 - 300 K, give new insight into the reaction mechanism. At the lowest temperature studied, 86 K, H2 formation is still ecient, while loss of water molecules is exceedingly slow, at a rate of less than 1 103 s1 . This shows that the barrier for the redox reaction is small, and that the V (H2 O)+ clusters are only observable on the ICR time n scale because the H2 formation pathway is very complicated, making the reaction highly improbable. Temperature resolved measurements of the rate constants of the black body radiation induced processes allow the extraction of activation energies via master equation modelling [6],[7]. It is shown that the standard single-well approach is insucient to describe the phase transitions occurring in this process. Successful modeling is achieved by explicit consideration of multiple phases.
[1]G. Niedner-Schatteburg and V. E. Bondybey, Chem. Rev. 100, 4059 (2000). [2]V. E. Bondybey and M. K. Beyer, Int. Rev. Phys. Chem. 21, 277 (2002). [3]O. P. Balaj, C.-K. Siu, I. Balteanu, M. K. Beyer, and V. E. Bondybey, Int. J. Mass Spectrom. 238, 65 (2004). [4]B. S. Fox, O. P. Balaj, I. Balteanu, M. K. Beyer, and V. E. Bondybey, Chem. Eur. J. 8, 5534 (2002). [5]B. S. Fox, I. Balteanu, O. P. Balaj, H. C. Liu, M. K. Beyer and V. E. Bondybey, Phys. Chem. Chem. Phys. 4, 2224 (2002). [6]W. D. Price, P. D. Schnier, R. A. Jockusch, E. F. Strittmatter, and E. R. Williams, J. Phys. Chem. B 101, 664 -673 (1997). [7]R. C. Dunbar, Mass Spectrom. Rev. 23, 127-158 (2004).
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Probing Stepwise Hydration by Gas Phase Vibrational Spectroscopy

Knut R. Asmis1 , Daniel J. Goebbert1 , Gabriele Santambrogio2 , Jia Zhou3 , Etienne Garand3 , Jerey Headrick4 , Mark A. Johnson4 , Daniel M. Neumark3,5 1. Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin, Germany 2. Institut fr Experimentalphysik, Freie Universitt Berlin, Berlin, Germany 3. Department of Chemistry, University of California, Berkeley, CA, USA 4. Sterling Chemistry Laboratory, Yale University, New Haven, CN, USA 5. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA
There is an ongoing eort, spanning all branches of the physical sciences, to obtain a detailed understanding of how ions are solvated in aqueous media. Infrared spectroscopy has been an important tool in this eort, not only for condensed phase studies, but also to investigate gas-phase species. Such studies help to elucidate the structural motifs that evolve as the number of solvent molecules changes. Here we report gas-phase infrared multiple photon photodissociation (IRMPD) spectra for two dierent types of solute-solvent systems: the hydrated electron clusters (H2 O) 1550 and hydrated sulfate dianion clusters SO2 (H2 O)324 . IRMPD spectra of these clusters, collisionally 4 cooled to 20 K, were obtained using radiation from the Free Electron Laser for Infrared eXperiments, FELIX [1], from 575 - 1800 cm1 . Hydrated electrons play an important role in radiation chemistry and various biological processes. Finite water cluster anions [2] have drawn considerable attention, as they represent potential model systems for characterizing the water network accommodating the excess electron under well controlled conditions and as a function of size. One of the central questions is related to the minimum cluster size required to accommodate the extra electron within the water cluster. In small water clusters the extra electron predominantly resides on the outside of the cluster and is bound by mainly a single water molecule (AA-binding motif) [3]. Our experiments suggest that the AA-binding motif survives in clusters containing up to 50 water molecules and that the transition from external to internal solvation of the excess electron proceeds gradually. Hydrated sulfate dianions are of paramount importance in diverse branches of science ranging from the homogeneous nucleation of ice particles by sulfate aerosol in the upper troposphere to the essential function of sulfate ions in many metabolic and cellular processes in vivo. IRMPD spectra of SO2 (H2 O)n complexes were measured in the region of the stretching and bending modes of the 4 sulfate core as well as characteristic intra- and intermolecular water modes, allowing an unprecedented, atomic level insight into structure and bonding of these species. The antisymmetric stretch mode 3 of the sulfate ion at 1100 cm1 acts as sensitive probe for the overall solvation geometry. In a symmetric environment, like in solution, this threefold degenerate mode leads to a single band in the IR spectrum, while asymmetric solvation, like for n=3, leads to symmetry lowering, lifting of the degeneracy and splitting of this band into its three components. On the other hand the water bending motion (1700 cm1 ) as well as intermolecular librational modes (800 cm1 ) are particular sensitive to the underlying nature and strength of the hydrogen bonding interaction [4].
[1]D. Oepts, A.F.G. van der Meer, P.W. van Amersfoort, Infrared Phys. Technol. 36, 297 (1995). [2]V. Coe,G.H. Lee, J.G.Eaton, S.T. Arnold, H.W. Sarkas, K.H. Bowen, C. Ludewigt, H. Haberland, D.R. Worsnop, J. Chem. Phys. 92, 3980 (1990). [3]N. I. Hammer, J.-W. Shin, J.M. Headrick, E.G Diken, J.R. Roscioli, G.H. Weddle, M.A. Johnson, Science 306, 675 (2004). [4]J. Zhou, G. Santambrogio, M. Brmmer, D.T. Moore, L. Wste, G. Meijer, D.M. Neumark, K.R. Asmis J. Chem. Phys. 125 111102 (2006).
34
TALKS
Interaction of hydrogen with graphitic nanostructures and hydrogen storage

Julio A. Alonso, Ivan Cabria, Maria J. Lopez Department of Theoretical, Atomic and Optical Physics, University of Valladolid, 47011 Valladolid, Spain
In the near future hydrogen could replace gasoline in cars, and prototypes using electric motors that obtain the energy from the reaction of hydrogen with atmospheric oxygen have already been developed by most car manufacturers. The main remaining challenge is to develope an eective way of storing the required amount of hydrogen in the tank of a car. A gravimetric hydrogen capacity of 6 % in weight and a volumetric capacity of 0.045 kg H2 /L are the targets established for 2010 by the Department of Energy of the USA. Another practical requirement is that hydrogen has to be easily adsorbed and desorbed at room temperature and moderate pressures. One of the storage methods that have been proposed is the physisorption of molecular hydrogen on graphitic materials with high specic surface area. Thermodynamic estimations indicate that an adsorption energy of 300-400 meV per molecule should be necessary to obtain ecient cyclic adsorption/desorption of hydrogen at room temperature and normal pressures. We have performed Density Functional calculations of the adsorption of molecular hydrogen on graphene layers and on the external surface of single-walled carbon nanotubes. In those cases, binding energies are close to 100 meV/molecule. The binding energies can be increased in two ways. One is by doping the nanotubes. We have found (see Figure 1) that doping with lithium increases the binding energies by a factor of two. The other is by adsorption of the hydrogen inside small nanopores. Models of nanopores are the internal part of a carbon nanotube and the space between two parallel graphene layers with a separation somehow increased with respect to the distance in graphite (slitpores). In that case, there is also an increase of the binding energy by a factor of two. Consequently, the combination of these two eects appears to oer a promising route for obtaining the required values of the adsorption energies. A statistical mechanical model for adsorption inside slitpores will be presented, which can be compared to experimental results for hydrogen storage on nanoporous carbon materials.
Figure 1: Molecular hydrogen adsorption curve on pure and Li-doped graphene layers.
35
TALKS
Understanding proton and electron hydration at the molecular level through cluster spectroscopy
Mark Johnson Department of Chemistry, Yale University, New Haven, USA
Two of the oldest problems in aqueous chemistry involve solvation of the elementary charges. Both of these species are anomalous solute ions in the sense that they can become entirely or partially incorporated into the fabric of individual water molecules or delocalized into more extended networks of water molecules as the medium is introduced in a step-wise manner. We describe how size-selected cluster spectroscopy provides detailed pictures of how these transformations occur. The excess proton problem is challenging because the extent of charge delocalization is network morphologydependent, and these changes result in dramatic stepwise changes in the spectroscopic signatures associated with the embedded charged species. The excess electron, on the other hand, yields a very specic and unique spectroscopic signature in the bending region of the vibrational spectrum that results from its accommodation largely by one water molecule. The challenge in the hydrated electron case, therefore, becomes one of following how this robust motif in the small cluster regime evolves into the bulk hydrated electron. The current status of the "surface vs internal" solvation morphology will be discussed.
36
TALKS
Abrupt and Gradual Transitions in Size Dependent Properties of Clusters: Form Mercury to Protons.
Bernd von Issendor1 , Ori Cheshnovsky2 1. Fakultt fr Mathematik und Physik, Universitt Freiburg, Stefan-Meier-Strae 19, 79104 Freiburg, Germany 2. School of Chemistry, The Beverly and Raymond Faculty of Exact Sciences, Tel aviv University, 69978 Tel Aviv, Israel
We critically review the issue of Metal to Insulator Transitions in metal clusters [1], in view of our new photoelectron spectroscopy (PES) studies on bivalent Zn clusters [2]. We show that zinc n clusters in the size range of n=3-117 exhibit a distinct transition in their electronic structure characteristics as a function of their size. At small sizes up to n=18 the clusters follow the Bloch-Wilson picture of the development of a metal from closed-shell atoms, exhibiting a gradual decrease of the gap between the fully occupied s band and the empty p band. For large sizes (n>32 ) valence electrons probably fully delocalize. This leads to an almost perfect free-electron density of states, as predicted by standard free-electron models and as supported by comparison to the PES obtained on sodium clusters. Based on these and other results we suggest a rened view on the gradual nature of Metal to Insulator Transitions in clusters. In contrast we present new observations, showing critical size behavior of proton transfer from a solvent cluster to solute anion.
Figure 1: The size dependence of the band gap at the EF of dierent cluster families as obtained from PES on cluster anions. The band gaps are plotted as a function of the number of valence electrons in the negatively charged clusters. The gaps have been normalized to the respective bulk EF of the materials and are shown as a function of the inverse cube root of the electron number, which is proportional to the inverse cluster radius.
[1]B. von Issendor, O. Cheshnovsky, Annu. Rev. Phys. Chem., 56, 549 (2005). [2]Kostko, O.; Wrigge, G.; Cheshnovsky, O.; von Issendor, B. J. Chem. Phys. 123,221101 (2005).
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TALKS
Matter wave interferometry with massive systems: Foundations, applications and perspectives for cluster physics
Markus Arndt Fakultt fr Physik, Universitt Wien, Wien, Austria
Matter wave interferometry with mesoscopic systems is driven by the desire to explore the experimental limits of quantum mechanics and also to test some new non-standard models predicting fundamental limits to the masses or times over which matter wave coherence may be observed. The talk gives a brief review over recent developments in matter wave interferometry, with large neutral objects, presents new applications for molecule metrology and molecule lithography and points to open challenges in the manipulation of large biomolecules and massive clusters.
38
TALKS
Chemistry and spectroscopy of gold and silver: X-ray activated growth studies of small clusters in stable soda lime silicate glasses
K. Rademann Humboldt-Universitt, Institut fr Chemie Brook-Taylor-Strae 2, D-12489 BERLIN, Germany
The very early stages of cluster formation allow the control of nano-particle formation and deposition in dierent environments. Especially, nobel metal-clusters are important study objects for basic research, catalysis [1] and modern chemical and optical applications. Of particular interest is the oxidation and reduction of gold clusters on silica [2], and its optical properties [3] Here we report on gold and silver clusters with narrow size distributions in soda lime silicate glasses. The clusters can be generated on demand by BESSY X-ray assisted activation of metal containing glass samples and a subsequent annealing process. This way, noble metal clusters even smaller than one nanometer become accessible. These systems reveal extraordinary optical properties like high quantum yield photoluminescence [4]-[5].
[1]G. J. Hutchings, Catalytic Science Series, Vol. 6: Catalysis by Gold, ed. by G. C. Bond, C. Louis, D. T. Thompson, Imperial College Press, 2006 [2]D. C. Lim, R. Dietsche, M. Bubek, G. Gantefr, Y. D. Kim ChemPhysChem 2006, 7, 1909-1911 [3]J.-M. Antonietti, M. Michalski, U. Heiz, H. Jones, K. H. Lim, N. Rsch, A. D. Vitto, G. Pacchioni; "Optical Absorption Spectrum of Gold Atoms Deposited on SiO2 from CRDS" Phys. Rev. Lett. 94, 213402 (2005) [4]Goerner, W., Eichelbaum, M., Matschat, R., Rademann, K., Radtke, M., Reinholz, U., Riesemeier, H. "Nondestructive investigation of composition, chemical properties and structure of materials by synchrotron radiation" INSIGHT 48 (9): 540-544 SEP 2006 [5]M. Eichelbaum, K. Rademann, R. Mller, M. Radtke, H. Riesemeier, W. Grner "Zur Chemie des Goldes in Silicatglsern: Untersuchungen zum nicht-thermisch aktivierten Wachstum von Goldclustern" Angew. Chem., 117, 8118-8122 (2005) "On the Chemistry of Gold in Silicate Glasses: Studies on a Nonthermally Activated Growth of Gold Nanoparticles" Angew. Chem. Int. Ed., 44, 7905-7909 (2005) [6]M. Eichelbaum, K. Rademann, W. Weigel, B. Lchel, M. Radtke, R. Mller "Gold-Ruby Glass in a New Light: On the Microstructuring of Optical Glasses With Synchrotron Radiation" Gold Bulletin, 2007, accepted
39
Thursday - Cluster Chemistry
TALKS
THURSDAY - CLUSTER CHEMISTRY
Catalytically active gold: from nano-particles to ultra-thin lms

Mingshu Chen and D. Wayne Goodman Department of Chemistry, Texas A&M University College Station, TX 77842-3012, USA
Ordered gold (Au) (1x1) mono- and (1x3) bi-layer lms have been synthesized on a titania ultra-thin lm grown on a Mo(112) surface [1]. The Au (1x3) bi-layer lm has a signicantly higher catalytic activity for carbon monoxide oxidation than does the Au (1x1) mono-layer lm. This discovery is a key to understanding the nature of the active site and structure of supported Au catalysts. Furthermore, it is the rst observation of Au completely wetting an oxide surface, and demonstrates that ultra-thin Au lms on an oxide surface have exceptionally high catalytic activity, comparable to the activity observed for Au nanoparticles [2].
[1]Chen, M. S.; Goodman, D. W., Accts. Chem. Res., 2006, 39, 739. [2]Chen, M. S.; Goodman, D. W., Science 2004, 306, 252; Valden, M.; Lai, X.; Goodman, D. W., Science 1998, 281, 1647.
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TALKS
Thermochemistry and Reactivity of Transition Metal and Metal Oxide Clusters

F. Liu, L. Tan, S. Liu, P. B. Armentrout 1. Department of Chemistry, University of Utah, 315 S. 1400 E. Rm 2020, Salt Lake City, UT 84108, USA
In our work, we have examined the kinetic energy dependences of the reactions of Fe+ , Co+ , and Ni+ n n n (n = 2 - 15) with D2 , O2 , N2 , CD4 , and ND3 in a guided ion beam tandem mass spectrometer over the energy range of 0 - 10 eV. Metal cluster cations are formed in a laser vaporization/supersonic expansion source and reactions are performed under single collision conditions. The kinetic energy dependences are analyzed to determine thresholds for various primary and secondary reactions. From these thresholds, bond energies for iron, cobalt, and nickel cluster cation bonds to D, O, N, C, CD, CD2 , CD3 , ND, ND2 , and ND3 have been determined. For the atomic systems, e.g., D and O, bond energies to modest size metal clusters (10 - 15 atoms) rapidly converge to values equivalent to bulk phase values. Thus, values for the molecular fragments provide some of the very FIRST data for the thermochemistry of such species bound to surfaces, information that is largely non-existent even though these are key intermediates in a variety of catalytic processes. Recent extensions of this work have examined the collision-induced dissociation of Fex O+ (x = 1 - 6) clusters, and have y elucidated the thermochemistry of several non-stoichiometric combinations.
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TALKS
Many Faces of Aromaticity in Clusters

Alexander I. Boldyrev Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322, USA
Today there is no simple chemical bonding model allowing us to use the "paper and pencil" approach for predicting global minima and low-lying isomers of homoatomic and heteroatomic clusters. However some progress in developing such a model has been made in recent years. In the current presentation we demonstrate, that structure, stability and other molecular properties of clusters can be explained using multiple (, , , ) aromaticity, conicting aromaticity (simultaneous presence of aromaticity and antiaromaticity), or (, , , ) multiple antiaromaticity. Boron clusters, which are the most understood clusters in chemistry will be used as an example. The global aromaticity (or global antiaromaticity) can be assigned on the basis of the 4n+2 (or 4n) electron counting rule for either or electrons in the planar structures. We showed that pure boron clusters can have double ( and ) aromaticity (B , B4 , B+ , B+ , B8 , B2 , B , 3 5 7 8 9 B10 , B+ , and B+ ), double ( and ) antiaromaticity (B2 , B15 ); and conicting aromaticity 11 13 6 (-antiaromatic and -aromatic) (B ) or (-aromatic and -antiaromatic) (B14 ). On the basis of 5 our understanding of chemical bonding in all-boron clusters we propose which clusters could potentially be new ligands and building blocks in chemistry. In addition to boron clusters we will show how aromaticity/antiaromaticity can be used to describe aluminum, silicon, and other main group clusters.
45
TALKS
Spectroscopy of biomolecules and cluster-biomolecules complex

M. Broyer Universit Lyon 1; CNRS; LASIM UMR 5579, bt. A. Kastler, 43 Bd du 11 Novembre 1918, F69622 Villeurbanne Cedex, France
Various methods to study complex molecules and of biomolecules will be presented. Firstly we will show how the conformation of complex molecules can be deduced from electric dipole measurements. This method will be illustrated by recent results on polypeptides and disubstitued benzene molecules. Then we present recent photo-dissociation experiments performed on biomolecules stored in a quadrupole ion trap. Information on the molecular structure can be obtained from the depletion spectrum as well as from the fragmentation channels. In the case of Tryptophan silver complex + (W Agn ), two classes of structure, zwitterionic and charge solvated, can be identied and are correlated to two dierent fragmentation spectra. Finally the photodetachement of peptides and DNA polyanions are investigated. The formation of radical anions and the mechanism of photodetachement are discussed.
46
TALKS
Size Selected Metal Cluster Surface Chemistry

David M. Rayner Steacie Institute for Molecular Sciences, National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario, K1A 0R6 Canada
The structure-specic dynamics of chemical reactions taking place on the surface of isolated metal clusters have tantalized cluster science for a long time. From the early days we have been aware of dramatic size-variations in reactivity but have been largely blind to surface reactions that might follow the rate determining adsorption step. The promise of new insight into how particular arrangements of metal atoms can be highly eective and highly specic in promoting chemical change in nanoparticle based catalysis has been tempered by the limited structural information provided by traditional mass spectrometry. Our approach is to use free-electron laser infrared photodepletion spectroscopy to probe the structure of mass-selected metal cluster complexes. Vibrational spectroscopy allows us not only to establish structure but to determine the inuence of cluster constitution, size and charge on the adsorbate(s), to follow the eects of co-adsorption and to determine the extent of any chemistry (e.g. isomerization, dissociative adsorption, reaction with a co-adsorbed ligand) taking place on the surface of the cluster. By carrying out these experiments as a function of the cluster reactor temperature we aim not only to establish if we can control reactions on cluster surfaces but also to obtain quantitative thermodynamic information. Progress in this area will be discussed with specic emphasis on CO as both a probe and as a reactant.
47
TALKS
Size dependent reactivity of transition metal clusters

Stephanie Jaberg, Britta Pfeer, Tanja Walter, and Gereon Niedner-Schatteburg Fachbereich Chemie, TU Kaiserslautern, Germany gns@chemie.uni-kl.de
We report on recent progress in the ongoing research on transition metal clusters as pursuit by our Fourier-Transform-Ion-Cyclotron-Resonance (FT-ICR) apparatus. When stored within its ion trap the clusters may be exposed to rareed gases such as e.g. various hydrocarbon derivatives. The then persisting single collision conditions allow for the recording of reaction kinetics and for the quantitative determination of elementary reaction steps in operation. We found naked iron clusters to reveal a surprisingly size dependent lack of bimolecular reactivity towards aromatic hydrocarbons as well as towards some prospectively -directing ligands. We shall discuss these ndings in the light of possible interpretations. Further experiments on related clusters and molecules shall help to put forward an increasingly systematic understanding of the prevailing eects.
48
TALKS
Electron Spectroscopy of mass selected clusters: From fs lasers to the FEL

Wolfgang Eberhardt BESSY GmbH, Albert Einstein Str. 15, 12489 Berlin, Germany
Clusters exhibit unique materials properties which dier largely from the corresponding bulk solids. Furthermore, these properties also show strong and non-monotonous variations with the size of the particles. Most widely investigated properties are the chemical reactivity as well as the electronic and magnetic properties, since all of these oer a unique potential for applications. Another unique feature of clusters is that the energy relaxation mechanisms and the dynamics are also quite dierent than in bulk solids. Partly this is due to the fact that an excited electronic state can distribute the excitation energy only over a very limited number of degrees of freedom. Furthermore, even if the excitation energy is delocalized over various degrees of freedom, it still remains localized to the spatially conned region of the cluster itself. Accordingly unusual relaxation mechanisms such as the evaporation of atoms or the delayed emission of electrons are quite common in clusters, whereas they are rarely observed in solids. Using fs pump-probe electron spectroscopy of mass selected clusters, we have explored these relaxation processes of electronically excited states in Au clusters. The phenomena observed depend strongly on the size of the cluster and range from electron-electron to electron-phonon scattering and from vibrational wavepacket oscillations to a quasi melting of the cluster. Apart from these electronic relaxation processes, fragmentation of the cluster is also observed. This opens the path to the eld of femtochemistry. So far however only indirect dissociation processes have been observed. Presently this type of spectroscopy is limited by the photon energies available from laboratory laser sources. However the new soft X-ray light sources such as the VUV-FEL at DESY and the planned BESSY-FEL oer a unique potential to expand these studies to include not only the complete valence electronic structure but also to core level spectroscopy, which is a sensitive probe of the local geometry and site specic chemistry.
49
Posters - Session A
Clusters and Biomolecules
POSTERS - SESSION A
A1
Ionization potential of sodium and imidazole in small water clusters - ab-initio molecular dynamics study
Lukasz Cwiklik, Pavel Jungwirth Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic and Center for Biomolecules and Complex Molecular Systems, Flemingovo n. 2, Prague, 16610, Czech Republic
We studied water clusters of sodium and imidazole employing Born-Oppenheimer ab-initio molecular dynamics simulations. In the case of sodium we investigated clusters consisting of 32 water molecules. In these simulations collisions of neutral sodium atom with water clusters were studied in order to investigate the process of ionization of sodium atom and delocalization of its valence electron. In the trajectories we observed ionization process, however, the resulting excess electron density was not fully delocalized. Calculated vertical ionization potential was changing from the value corresponding to the ionization of sodium atom in the gas phase (for initial stages of simulations, i.e., before the collision with water cluster) to the values comparable with experimental ionization potential of sodium in water clusters. In the studies concerning imidazole we investigated clusters with changing number of water molecules. We started with systems consisting of one imidazole molecule and one up to ve solvent molecules. We performed ab-initio molecular dynamics simulations in order to identify minimal energy congurations. Then the minima were found and vertical ionization potential values were calculated. We also studied clusters of imidazole and 20 water molecules in order to use snapshots from these trajectories in higher-level ab-initio calculations of ionization potential.
55
A2
POSTERS - SESSION A
Imaging for molecular beam deection experiments: Asymmetric rotors in electric eld-inuence for internal torsions.
M. Abd El Rahim1 , R. Antoine2 , D. Rayane2 , Ph. Dugourd2 and M. Broyer2 1.Institut fr Experimentalphysik, Freie Universitt Berlin, Arnimallee 14, D-14195, Berlin, Germany 2. Laboratoire de Spectromtrie Ionique et Molculaire, UMR 5579 (Universit Lyon I et CNRS), Bt. A. Kastler, 43 Bd du 11 Novembre 1918, 69622 Villeurbanne Cedex, France
We have developed a position sensitive detection coupled to a high resolution time of ight mass spectrometer and to an electrostatic deector. This experimental setup allows us to measure the electric dipole moment of molecules in the gas phase. With this new type of detection, we succeeded to uncouple the two measurements: mass-position of beams molecules. Performance of this setup was demonstrated over a large mass range with cesium bromide clusters. Using this direct imaging, electric beam deection experiments on aminobenzonitrile and (dimethylamino) benzonitrile molecules have been performed. They are used as prototypes to study the inuence of the asymmetry and rotation-vibration couplings in deection experiments. Experimental results were compared to those of ab initio calculations in the frame of the rigid rotor Stark eect and of the statistical linear response. This comparison show that the change in symmetry and the introduction of methyl groups lead to a transition from the rigid rotor response to the linear response.
Figure 1: MDMABN beam proles (along the axis of electric eld) obtained respectively for a null and non null electric eld. The tensions above indicate the potential dierences across the deector
[1]M. Abd El Rahim et al, Review of scientic instruments, 75, 12, 5221 (2004). [2]M. Abd El Rahim et al, Journal of Physical Chemistry A, 109, 8507 (2005). [3]R. Antoine et al, Journal of Physical Chemistry A, 110, 10006 (2006).
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POSTERS - SESSION A
A3
Isomer specic studies of the Zundel cation (H2 OH+ OH2 )

Ben M. Elliott, J. Robert Roscioli, Joseph C. Bopp, Jerey M. Headrick, Laura McCunn, Nathan Hammer2 , Mark A. Johnson1 1. Department of Chemistry, Yale University, 225 Prospect St., New Haven, Ct 06520, USA 2. Department of Chemistry, University of Massachusetts, Amherst, MA 01003, USA
Although the vibrational spectrum of the Zundel cation (H5 O+ ) is simple, consisting of a pair of 2 doublet transitions at 1000 and 1700 cm1 , the assignment of the mechanical origin of this pattern has proven remarkably dicult. One problem certainly arises from the strong anharmonicities present owing to the coupling of the shared proton motion to the soft modes nominally associated with wagging and twisting of the anking water molecules. In order to address these issues, we report progress on a new generation of experiments where we follow how the bands evolve upon H/D substitution in such a way that the single hetero-isotope lies in the shared position, while the dominant isotope occupies the four free OH positions on the two water molecules. Because the relevant singly substituted target species occur in two isomeric forms depending on whether this atom lies in the shared or free position, we carry out isomerselective spectroscopy using population modulation with two IR lasers in a tandem time-of-ight arrangement. Lines of the spectra relating to specic positions of the unique isotope are selected by the initial IR laser, and the selected isomer is then interrogated by a second IR laser pulse.
Figure 1: Calculated structure of the Zundel cation.
57
A4
POSTERS - SESSION A
Laser desorption source for large molecules

Markus Marksteiner, Lucia Hackermller, Gregor Kiesewetter, Hendrik Ulbricht and Markus Arndt Fakultt fr Physik, Universitt Wien, Boltzmanngasse 5, A - 1090 Wien, Austria
The experimental proof of the wave nature for massive particles is an important demonstration for the validity of the foundation of physics. With a Talbot-Lau interferometer consisting of three mechanical gratings we could show the wave like behaviour of fullerenes and special uorinated fullerenes C60 F48 with a mass of 1630u (Hackermller et al. PRL 91, 90408 (2003)). In order to do interferometry of high mass biomolecules a laser desorption source was built and tested with the two biomolecules tryptophan (204u) and gramicidin (1880u). The molecules are desorbed by a nanosecond laser pulse and cooled in a mixing channel via collisions with a supersonic expanding gasbeam, resulting in a beam of neutral molecules, that can be photopostionized for time of ight detection. Experiments showed a sucient signal for tryptophan and gramicidin, which should allow the combination of the source with the interferometer. Photo-ionization has been tested at two dierent wavelengths, namely at 266 nm and 157 nm. In the case of tryptophan the ionization signal was saturated in both cases, whereas for gramicidin the signal recorded at 157 nm photoionization wavelength is 5 times higher than that at 266 nm. We study the dependence of the ionization signal both on the desorption wavelength, for dierent carrier gases and dierent cooling modes, and the functional dependence on the ionization intensity. Experiments with molecules at even higher mass, such as insulin (5700 u), showed, that these particles generally strongly fragment during desorption and/or ionization and they did not reveal any signicant intact mother ion. Metal clusters are an interesting alternative to biomolecules for matter wave experiments. They have a signicantly lower ionization energy and it is known that they may undergo single-photon ionization.
58
POSTERS - SESSION A
A5
Formation of a Covalent Bond upon Electron Attachment to van der Waals Complex
Sang Hak Lee, Nam Doo Kim, Dong Gyun Ha, Ki Wook Hwang, and Seong Keun Kim School of Chemistry, Seoul National University, Seoul 151-747, Korea
Following our earlier nding of the covalent bond formation in the van der Waals complex of pyridine and CO2 upon electron attachment, we extended our study to diazines and s-triazine. In the anion complexes between pyrazine and CO2 , the 1:1 and 1:2 complexes showed a drastic increase in vertical detachment energy (VDE) of 2.0 and 4.3 eV, respectively, apparently because an extended -network is formed through the aforementioned covalent bond bridge between CO2 and pyrazine. In pyrimidine and pyridazine, the VDE shifts by 2.0 eV upon covalent bond formation with the rst CO2 and by 0.2 eV when simply solvated by the second CO2 . s-triazine showed a similar behavior with the rst two CO2 s, but the third CO2 increased the VDE by another 2.0 eV. It appears that the covalent bond formation is sterically hindered in the 1:2 complexes pyrimidine and pyridazine unlike the case of pyrazine, while such steric hindrance is overcome in the 1:3 complexes of s-triazine by "forced" binding of the third CO2 . Optimized geometry of the anion complexes obtained at the B3LYP/6-31++G and MP2/6-31++G level supports the above experimental results, showing that the interaction between azabenzene and CO2 undergoes a drastic change in its bonding nature upon electron attachment.
[1]Michael J. DeLuca et al., J. Chem. Phys, 88, 5857(1988). [2]S. Y. Han et al. J. Chem. Phys. 113, 596 (2000). [3]Holger Schneider et al., J. Chem. Phys, 123, 074316(2005).
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A6
POSTERS - SESSION A
Quantum Building Blocks Concept for Biomacromolecules

O. I. Obolensky, I. A. Solovyov, A. V. Solovyov, W. Greiner Frankfurt Institute for Advanced Studies, Max-von-Laue-Str. 1, 60438 Frankfurt am Main, Germany
The idea of representing complex molecular structures as sets of building blocks is not new. It allows one to reduce drastically the volume of the conformational space, since ne details are integrated out producing renormalized eective interactions between the surviving collective degrees of freedom (the building blocks). The number of the degrees of freedom and accuracy of the eective interactions range widely depending on the system under consideration and on simplicity of the model. This strategy has led to signicant breakthroughs in understanding structural properties of complex systems. For example, in the protein folding problem such phenomena as nucleation of the hydrophobic core or existence of a molten globule state can be explained with the building blocks concept [1]. The shortcoming of this approach is in the lack of predictive power for the de novo structure determination stemming from the excessive simplicity of the interaction potentials used. We present here the formalism and the rst results of quantum building blocks calculations in which the interaction potentials are calculated at an ab initio quantum mechanical level. We have performed density functional theory calculations of multidimensional potential energy surface for alanine-alanine interactions. In our approach the potential energy of the interaction depends on six variables, three of which describe the relative position and the other three describe the mutual orientation of the coordinate systems associated with each amino acid, see the gure. Using the quantum building blocks approach we found the global energy minimum structures of several Ala oligopeptides. The found structures are in a good agreement with our previous complete quantum mechanical analysis [2].
We acknowledge partial nancial support from the European Commission (project EXCELL).
[1]A. Kolinski, J. Skolnick, Polymer, 45, 511 (2004). [2]I. A. Solovyov, A. V. Yakubovich, A. V. Solovyov, W. Greiner, Phys. Rev. E, 73, 021916 (2006)
60
POSTERS - SESSION A
A7
Solvation of amino acids: From the isolated molecule to the solution.

M. N. Blom1 , I. Compagnon1 , N. Polfer1 , G. v. Helden2 , G. Meijer2 , S. Suhai3 , B. Paizs3 and J. Oomens1 1. FOM Institute "Rijnhuizen", Edisonbaan 14, 3439 MN Nieuwegein, The Netherlands. 2. Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany. 3. German Cancer Research Center, Im Neuenheimer Feld 580, 69120 Heidelberg, Germany.
In contrast to aqueous solutions, amino acids adopt a non-zwitterionic structure in the gas phase. To answer the question on how many solvent molecules are required to stabilize the zwitterionic structure, neutral tryptophan-solvent complexes (Trp(H2 O)16 , Trp(D2 O)16 and Trp(MeOH)19 ) are probed by infrared spectroscopy and density functional theory (B3LYP/6-31+G ). The structural identication is performed based on diagnostic vibrations, such as the C=O stretch, the CO-H bending mode, the asymmetric COO stretch and the weaker NH+ bending mode (1300-1850 3 cm1 ). Small solvated complexes (n=1-4) are found to be non-zwitterionic and exhibit two distinctive conformeric motifs. Starting with 5 solvent molecules a well separated COO band was found for Trp(MeOH)59 and a shift of the CO stretch frequency was detected for Trp(H2 O)56 and Trp(D2 O)56 displaying the appearance of zwitterionic structures. Moreover, the convergence toward the FTIR spectrum of tryptophan in methanol is clearly observed.
61
A8
POSTERS - SESSION A
Inelastic electron interaction (ionization/attachment) with biomolecules embedded in superuid helium droplets
S.Deni, F. Zappa, I. Mhr, T.D. Mrk, P. Scheier 1. Institut fr Ionenphysik und Angewandte Physik, Leopold-Franzens-Universitt Innsbruck, Technikerstrasse 25, A-6020 Innsbruck, Austria
The extensive number of spectroscopy studies with doped helium droplets shows impressively the ability of superuid helium droplets to be a perfect matrix for the preparation of cold targets and the formation of complex fragile species [1]. In contrast, the inelastic electron interaction with doped helium droplets is much less studied. This fact is rather surprising as clusters of biomolecules can be formed from the gas phase by embedding single biomolecules into the cold droplets. It is known that electrons can induce ecient DNA damage and in cells secondary electrons are produced with high abundance by ionizing radiation. Thus the underlying chemical and physical processes of the inelastic electron interaction with isolated and also solvated biomolecules is of relevance for the investigation of DNA damage by ionizing radiation and moreover, of fundamental interest in physical chemistry. Our group has constructed a helium cluster source which was initially used to study the electron impact ionization of pure helium clusters [2], as well as their metastable decays [3]. Recently we modied our setup by adding a pick up chamber with oven, pick up cell and external gas inlet which allows the embedment of various molecules in cold superuid helium droplets. The neutral mixed clusters are ionized in a Nier type ion source and mass analyzed by a two sector eld mass spectrometer. First studies of the pick up process have been performed with DNA nucleobases adenine and thymine which are well studied in the gas phase. Several interesting phenomena occurred, e.g. we could observe parent anions for adenine and thymine which is not the case in the gas phase [4]. In this contribution we will present in detail the experimental setup for our pick-up experiments and summarize our results concerning the inelastic electron interaction with DNA nucleobases embedded in cold helium droplets. The pick-up experiments have been continued by embedding the amino acid valine, water and very recently even C60 in the helium droplets. From these measurements we can characterize the ionization/attachment process for the dierent species when inside the He droplets. This work was partially supported by FWF, Wien, the European Commission, Brussels (ITS-LEIF) and the Brazilian agency CNPq.
[1]J. [2]S. [3]S. [4]S.
P. Toennies, A. F. Vilesov, Angew. Chem. Int. Ed. 43 2622 (2004). Deni, M. Stano, A. Stamatovic, P. Scheier, T. D. Mrk, J. Chem. Phys. 124 054320 (2006). Feil, K. Gluch, S. Deni, F. Zappa, O. Echt, P. Scheier and T.D. Mrk, Int. J. Mass. Spectr 252 166 (2006). Deni, F. Zappa, I. Mhr, J. Lecointre, M. Probst, T. D. Mrk, P. Scheier, Phys. Rev. Lett., 97 043201 (2006)
62
POSTERS - SESSION A
A9
Enantioselective Nickel Mediated Gas-Phase Dehydrogenation of Secondary Alcohols

Francesca Novara1 , Detlef Schrder
1,2
, Helmut Schwarz1
1. Institute of Chemistry, Technical University Berlin, Strasse des 17. Juni 135, D-10623 Berlin, Germany 2. Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo nam. 2, 16610 Prague 6, Czech Republic
Enantioselectivity remains an intriguing and challenging topic of investigation due to its importance in asymmetric synthesis and for its distinct role in biological systems. Gas-phase studies can provide an understanding of the intrinsic properties underlying the mechanisms of chiral discrimination.[1][3] Here, we report on enantioselective bond activations observed upon collision-induced dissociation (CID) of chiral Ni complexes of the generic composition [(BINOLate)Ni(CH3 (CHOH)R)]+ , where BINOLate corresponds to singly deprotonated R- or S-bis-2-naphthol and R = n-C2 H5 , n-C3 H7 , n-C4 H9 , n-C5 H11 , n-C6 H13 and C6 H5 , respectively. Upon CID, the mass-selected nickel complexes lose either the entire alcohol ligand or undergo bond activation followed by loss of the corresponding ketone. When enantiomeric BINOLate ligands are combined with chiral secondary alcohols, the complexes become diastereomeric. Dierences in the branching ratios between the two channels for dierent diastereomeric complexes are observed and can serve as a measure for the chiral discrimination operative in the CH and OHbond activation processes.
Figure 1: Breakdown graph of the CID fragments of mass-selected (R-BINOL-H)Ni(R-1-phenylethanol)+ as a function of collision energy in the center- of-.mass frame. The chiral BINOLate ligand has been chosen as a stereochemical discriminator by analogy to wellknown asymmetric hydrogenation catalysts.[4] Thus, by reference to the principle of miscroscopic reversibility, the proposed system can be considered a model for the transition-metal catalyzed enantioselective hydrogenation of ketones.
[1]M. Speranza Adv. Phys. Org. Chem. 39, 147 (2004). [2]A. Filippi, A. Giardini, S. Piccirillo and M. Speranza Int. J. Mass Spectrom. 198, 137 (2000). [3]D. Schrder and H. Schwarz Int. J. Mass Spectrom. 231, 139 (2004). [4]R. Noyori and T. Okhuma Angew. Chem. Int. Ed. 40, 40 (2001).
63
Magnetism
POSTERS - SESSION A
A10
Magnetic and structural properties of mass-ltered 3d transition metal nanoparticles

Armin Kleibert1 , Johannes Passig1 , Joachim Bansmann2 , Renate K. Gebhardt3 , Furkan Bulut3 , Mathias Getzla3 , Karl-Heinz Meiwes-Broer1 1. Institute of Physics, Rostock University,Universittsplatz 3, D-18051 Rostock, Germany 2. Institute of Surface Chemistry and Catalysis , Ulm University, Albert-Einstein-Allee 47, D-89069 Ulm, Germany 3. Institute of Applied Physics, Dsseldorf University, Universittsstrasse, Dsseldorf, D-40225 Dsseldorf, Germany
Free clusters and nanoparticles are not just small pieces of material with physical properties nearly identical to the bulk. Their electronic, optical and magnetic properties are clearly size-dependent with a non-linear behaviour between the two general limits given by the atomic and the bulklike behaviour [1]. Recently, it was shown that even large iron nanoparticles with diameters of about 10 nm show magnetic orbital moments that signicantly deviate from the respective bulk properties [1],[2]. In this contribution we compare the magnetic properties of mass-ltered Fe, Co and FeCo nanoparticles being deposited onto dierent epitaxially grown thin lms. The crystallographic structure and morphology of the particles have been determined independently by means of electron diraction and high resolution transmission electron microscopy (HRTEM), respectively (cf. Fig. 1). The magnetic moments of the clusters have been measured in situ via X-ray magnetic circular dichroism (XMCD) after deposition onto ferromagnetic lms.
Figure 1: High resolution transmission electron microscopy images of individual Fe, Co, and FeCo nanoparticles with diameters of about 15 nm.
[1]J. Bansmann et al., Surface Science Reports 56, 189 (2005). [2]J. Bansmann and A. Kleibert, Appl. Phys. A 80, 957 (2005).
67
A11
POSTERS - SESSION A
Structure and Magnetism of La Clusters

Andrey Lyalin, Andrey Solovyov, and Walter Greiner Frankfurt Institute for Advanced Studies, Max von Laue Str. 1, 60438 Frankfurt am Main, Germany
We have performed a systematic theoretical investigation of optimized ionic structure, electronic and magnetic properties of La clusters within the size range N < 14 [1]. We found a giant enhancement of magnetism in La4 , La6 , and La13 clusters. We also found that the ground states of La2 , La3 , La5 , La7 , La9 -La11 , and La14 clusters possess nonzero magnetic moments, that ranged from 0.1 B to 1.0 B per atom. This clearly indicates that small La clusters display magnetic behavior, even though bulk La has no magnetic ordering. We show that magnetism in La clusters is governed by unpaired valence electrons, in contrast to the local-moment magnetism in clusters of heavy rareearth elements. In addition to the ground state isomers of La clusters we found an ensemble of energetically low-lying spin isomers. We predict an increase of the average magnetic moments for ensembles of La2 , La3 , La5 , La8 , La9 , La11 , La12 , and La14 clusters with temperature due to the thermal population of the spin isomers. For ensembles of La4 , La7 , and La13 clusters, the average magnetic moment decreases with temperature. Such an anomalous behavior of the magnetic moment with temperature can be detected in Stern-Gerlach deection experiments.
Figure 1: Binding energy per atom for the most stable La clusters (left); magnetic moments per atom for La clusters as a function of cluster size. Open circles present the results of experiment by Knickelbein [2] (b). This work is partially supported by the European Commission within the Network of Excellence project EXCELL, and by INTAS under the Grant No. 03-51-6170.
[1]A. Lyalin, A. V. Solovyov and W. Greiner, Phys. Rev. A 74, 043201 (2006). [2]M. B. Knickelbein, Phys. Rev. B 71, 184442 (2005).
68
POSTERS - SESSION A
A12
Ferromagnetism in Finite Mn Linear Chains

Andrey Lyalin, Andrey Solovyov, and Walter Greiner Frankfurt Institute for Advanced Studies, Max von Laue Str. 1, 60438 Frankfurt am Main, Germany
The study of evolution of magnetic properties from atoms to the bulk is important for the development of magnetic nanomaterials with specic properties and for understanding the fundamental principles of spin coupling in nite and low dimensional systems. In this work we report the results of a systematic theoretical investigation of optimized structure, electronic and magnetic properties of linear chains of Mn atoms and organometallic sandwich clusters M nN (C6 H6 )N +1 within the size range N 6 [1]. The choice of Mn is stipulated by the fact that the Mn atom possesses a large magnetic moment due to the half-lled 3d electron shell, and thus, manganese is a good candidate for strong nanomagnets. Our calculations are based on ab initio theoretical methods invoking densityfunctional theory with the gradient-corrected exchange-correlation functional of Perdew, Burke and Ernzerhof (PBEPBE). The standard LANL2MB basis set of primitive Gaussians have been used to expand the electronic orbitals formed by the 3s2 3p6 3d5 4s2 outer electrons of Mn (15 electrons per atom). We show that the nite linear chains of Mn atoms exhibit novel magnetic properties that dier from those of the corresponding Mn bulk and one-dimensional innite chains. Thus, we demonstrate that nite one-dimensional monoatomic chains of Mn atoms possess ferromagnetic order in spite of the fact that the most stable crystal structure of Mn exhibits antiferromagnetic behaviour. We demonstrate that magnetic ordering in nite linear chains depends on its length and therefore can be controlled by the xing chains geometry. We also predict enhancement of magnetism in organometallic sandwich clusters M nN (C6 H6 )N +1 .
Figure 1: Binding energy per atom for Mn6 linear chain as a function of multiplicity 2S+1 (right). Mulliken atomic spin densities for dierent spin isomers of Mn6 chain (left). Interatomic distances are given in angstroms. This work is partially supported by the European Commission within the Network of Excellence project EXCELL, and by INTAS under the Grant No. 03-51-6170.
[1]A. Lyalin, A.V. Solovyov and W. Greiner, in preparation for Phys. Rev. A (2007).
69
A13
POSTERS - SESSION A
Magnetic properties of mass selected, deposited alloy clusters

Michael Martins, Leif Glaser, Michael Wellhfer, Wilfried Wurth Institut for Experimental Physics, University of Hamburg, Luruper Chaussee 149, D-22761 Hamburg, Germany
Nano particles are promising new materials for ultra small magnetic storage devices. In particular mass selected clusters are good candidates for such applications, because their properties can be tailored by just changing the cluster size. In recent work properties as a function of the number of atoms per cluster have been studied [1],[2]. However, by changing also the composition of the clusters a much larger functional space will be available. For magnetic storage devices in particular a huge magnetic anisotropy is mandatory, to x the magnetization direction in space. This can potentially be realized by systems with a large orbital magnetic moment and a large spin-orbit coupling. Therefore, we have started experiments on small mass selected, deposited Con Ptm clusters on dierent magnetized substrates to study their orbital and spin moments size dependent. To probe the magnetic properties of the clusters the x-ray magnetic circular dichroism (XMCD) method is applied using synchrotron radiation. In gure 1 the XMCD spectra for several CoPtm cluster deposited on a thin magnetized Fe lm are shown. All spectra have been normalized to the same L2 dichroism intensity, so that the L3 dichroism signal reects directly the ratio of orbital/spin magnetic moment. By adding a single Pt atom to a Co atom the orbital/spin ratio is increasing by 60%, whereas addition of further Pt atoms decreases the ratio again. This shows, that tailoring a special property might be possible by choosing the right size and composition of a cluster. This work is performed within the framework of the Sonderforschungsbereich 668.
Figure 1: XMCD spectra of deposited CoPtm cluster at the Co L2 and L3 edges on a magnetized Fe lm. The spectra have been normalized to the same intensity at the L2 edge.
[1]J.T. Lau et al, Phys. Rev. Lett. 89, 57201 (2002). [2]M. Reif et al., Phys. Rev. B 72, 155405 (2005).
70
Metal Clusters
POSTERS - SESSION A
A14
Theoretical Study of Thermodynamical Properties and Phase Changes in Krypton Clusters

Ales Vitek Department of Physics, University of Ostrava, Ostrava, Czech Republic
The subject of our research has been a theoretical study of thermodynamical properties and phase changes in medium-size krypton cluster cations Kr+ , Kr+ and Kr+ , by means of Monte Carlo 12 13 14 simulations. The simulations have been performed for a broad range of cluster temperatures or internal energies. Single ionized rare gas clusters are heterogeneous systems. The positive charge is located on a small subunit (ionic core), involving 2-4 atoms, surrounded by a cloud of almost neutral atoms. The Kr+ cluster is extremely stable due to its closed-shell conguration. For a 13 deeper insight into the structural changes in Kr+ , it turned out to be interesting to focus on Kr+ 12 N and Kr+ cluster, in which one atom is absent from or added to the perfect symmetry conguration 14 of Kr+ . Single structural change has been detected prior to the evaporation. It has been proved that 13 the ionic core melts at higher temperatures than the neutral envelope. The intra-cluster interaction has been described by extended diatomics-in-molecules models with the inclusion of the spin-orbital coupling. Further, the diatomics-in-molecules models have been extended by inclusion of three-body polarization forces acting between two induced dipoles and three-body van der Waals forces.
73
A15
POSTERS - SESSION A
Electronic photodissociation spectroscopy in comparison with TDDFT calculations in the case of Au+ Arn (m=2-9,n=0-3) m
Alexia N. Gloess1 , Holger Schneider2 , J. Mathias Weber2 , Manfred M. Kappes1 1. Institut fr Physikalische Chemie, Universitt Karlsruhe, Germany 2. JILA, University of Colorado, Boulder, USA
We report on electronic photodissociation spectroscopy of Au+ Arn clusters (m = 4, 7-9; n = 0-3). m The spectra were obtained in the photon energy range between 2.14 eV and 3.35 eV in the case of Au+ and Au+ Ar and in the range between 2.14 eV and 3.02 eV for all other clusters. Photodissoci4 4 ation spectra were recorded by monitoring ion depletion upon photon absorption, yielding absolute photodissociation cross sections. The interpretation of the experimental data was performed by comparing the results with calculations of the electronic absorption spectra using time-dependent density functional theory based on cluster structures calculated with density functional theory with the functional B3-LYP as well as with ab-initio calculations at the MP2 level. These calculations have been extended to a cluster size of Au+ - Au+ and Au+ Arn (m = 4, 7; n = 1-3). m 2 9 The experimentally obtained electronic photodissociation spectra show a qualitative change between the size of m = 7 and m = 8. We compare the photodissociation spectra with the quantum mechanically calculated electronic absorption spectra. The observed change can be explained by the transition from two- to three-dimensionality of the clusters underlying structures.
74
POSTERS - SESSION A
A16
Far-infrared spectroscopy of small neutral silver clusters

Andr Fielicke, Ira Rabin, and Gerard Meijer Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin, Germany
The determination of the geometric structures of metal clusters is still one of the central goals of experimental cluster research. Infrared absorption spectroscopy as a fairly direct method to obtain structural information is very dicult, since the vibrational bands of metal clusters are in the farinfrared and have notoriously low IR intensities. Here, we report on the vibrational spectra of the neutral silver trimer and tetramer in the gasphase. IR spectra are obtained via Multiple Photon Dissociation Spectroscopy of their complexes with argon atoms. The focus is in particular on Ag3 , which has been studied intensively up to now, but for which the available data on the vibrational properties is rather controversial.[1] Our investigations on the isolated clusters provide direct and mass selective measurements of the infrared spectra and form the basis for the evaluation of the data from earlier studies. Further, by increasing the argon coverage we can obtain conditions similar to matrix embedding that is then reected in shifts of the vibrational frequencies towards the matrix values. In the present study, complexes of small neutral silver clusters with one or a few argon atoms are generated using a pick-up cluster source.[2] The vibrational spectra of Ag3 and Ag4 are recorded in the far-infrared between 100-220 cm1 using multiple photon dissociation spectroscopy of their complexes with Ar atoms. For Ag3 -Ar two IR active bands are found at 113 cm1 and 183 cm1 , for Ag4 -Ar one band at 163 cm1 and very weak IR activity at 193 cm1 are observed. This, together with recent theoretical studies, allows for a reassignment of the controversial vibrational data reported earlier for the bare Ag3 cluster. The inuence of the number of Ar atoms in the complexes on the frequency of the IR active modes is found to be minor. However, the low-frequency IR-active band of Ag3 shifts with increasing Ar coverage from 113 cm1 for Ag3 -Ar to about 120 cm1 for Ag3 -Ar4 , the value known for Ag3 embedded in rare gas matrices.[3]
[1]J. R. Lombardi and B. Davis, Chem. Rev., 102, 2431 (2002). [2]D. Ievlev, I. Rabin, W. Schulze, and G. Ertl, Chem. Phys. Lett., 328, 142 (2000); D. Ievlev, I. Rabin, W. Schulze, and G. Ertl, Eur. Phys. J. D, 16, 157 (2001). [3]A. Fielicke, I. Rabin, and G. Meijer, J. Phys. Chem. A, 110, 8060 (2006).
75
A17
POSTERS - SESSION A
Electric Deection Studies of Rhodium Clusters

Martin K. Beyer1 , Mark B. Knickelbein2 1. Institut fr Chemie, Sekr. C4, Technische Universitt Berlin, Strae des 17. Juni 135, 10623 Berlin, Germany 2. Chemistry Division, Argonne National Laboratory, Argonne, IL 60439, USA
The static electric dipole polarizabilities of rhodium clusters Rhn , n=5-28, have been measured [1] via a molecular beam deection method. Uniform high-eld beam deections, indicative of induced polarization, were observed for all Rhn except Rh7 and Rh10 which by contrast exhibited beam broadening and anomalously high eective polarizabilities. Analysis of the beam deection prole of Rh7 indicates that it possesses a permanent dipole moment of 0.240.02 D. Unlike the other clusters in the n=5-28 size range, the polarizability of Rh10 is observed to decrease with increasing source temperature. We attribute this temperature dependence to paraelectric behavior, suggesting that Rh10 is a uxional molecule possessing a dipole moment that spatially uctuates, uncorrelated with overall rotation.
[1]M. K. Beyer and M. B. Knickelbein, J. Chem. Phys. in print.
76
POSTERS - SESSION A
A18
Liquid-Liquid Coexistence in Gold Clusters: 2D or not 2D?

Pekka Koskinen1,2 , Hannu Hkkinen3 , Bernd Huber2 , Bernd von Issendor2 , and Michael Moseler1,2 1. Fraunhofer-Institut fr Werkstomechanik IWM, Whlerstrae 11, 79108 Freiburg, Germany 2. Fakultt fr Physik, Hermann-Herder Strasse 3, 79104 Freiburg, Germany 3. Department of Physics, NanoScience Center, University of Jyvskyl, 40014 Jyvskyl, Finland
The thermodynamics of gold cluster anions (AuN , N=11...14) is investigated using quantum molecular dynamics. Our simulations suggest that AuN may exhibit a novel, free-standing planar liquid phase which dynamically coexists with a normal three-dimensional liquid. Upon cooling with experimentally realizable cooling rates, the entropy-favored three-dimensional liquid clusters often supercool and solidify into the wrong dimensionality. This indicates that experimental validation of theoretically predicted AuN ground states might be more complicated than hitherto expected.
[1]P. Koskinen, H. Hkkinen, B. Huber, B. v.Issendor, and M. Moseler, Liquid-liquid coexistence in gold clusters: 2D or not 2D? Phys. Rev. Lett. 98, 015701 (2007).
77
A19
POSTERS - SESSION A
Mass-resolved Soft X-ray Ion Yield Spectroscopy of Free Transition Metal Clusters
J. T. Lau1 , M. Vogel1 , J. Rittmann1 , V. Zamudio-Bayer1 , T. Schadow1 , B. v. Issendor2 , and T. Mller1 1. Institut fr Optik und Atomare Physik, PN 3-1, Technische Universitt Berlin, Hardenbergstrae 36, D-10623 Berlin, Germany 2. Fakultt fr Physik/FMF, Albert-Ludwigs-Universitt Freiburg, Stefan-Meier-Strae 21, D-79104 Freiburg, Germany
Core level X-ray absorption spectroscopy is a valuable tool to investigate the unoccupied local electronic density of states with element specicity [1],[2]. Because of the local nature of inner shell excitation, the chemical environment and bonding of individual chemical elements can be studied. This is a great advantage, oering the exciting prospect of studying the electronic properties of individual constituents in doped or binary clusters. In a rst step towards this aim, mass resolved soft X-ray absorption of neutral, pure transition metal clusters was measured recently, using ion yield spectroscopy at the Berlin synchrotron radiation source BESSY. Neutral transition metal clusters are produced in a magnetron source, ionized by soft X-ray radiation, and detected by time-of-ight mass spectroscopy. High mass resolution up to m/m = 1500 is used to record transition metal cluster mass spectra while scanning the photon energy across the L2,3 absorption edges. Relaxation of the core excited state via Auger decay leads to multiply charged cluster ions. The charge state distribution of cluster ions after soft X-ray absorption is analyzed as function of cluster size and excitation energy in the vicinity of the L2,3 edges. Charge states extend from 1+ to 6+ with a maximum around triply and quadruply charged cluster ions, in line with experimental results on transition metal atoms. Photon energy dependent fragmentation of the cluster ions leads to apparent changes in the observed cluster size distribution with varying photon energy.X-ray absorption line shapes and branching ratios are almost bulk-like for medium sized clusters, whereas smaller clusters show a richer structure in their absorption lines. The size evolution of L2,3 X-ray absorption will be discussed for Tin , Vn , Con , and Nin clusters.
Figure 1: . Detail of a soft X-ray ion yield spectrum of neutral cobalt clusters with n/z =2021, recorded at 780 eV photon energy. Contributions of clusters with dierent z state are clearly discernible. Dashed line/markers: data; solid line: t to the data. All charge states contribute to n/z =20 and 21.
[1]O. Bjrneholm, F. Federmann, F. Fssing, and T. Mller, Phys. Rev. Lett. 74, 3017 (1995). [2]P. Piseri et al., New J. Phys. 8, 136 (2006).
78
POSTERS - SESSION A
A20
Interplay of Electronic and Geometry Shell Closures for Neutral and Charged Strontium Clusters
Andrey Lyalin, Ilia Solovyov , Andrey Solovyov, and Walter Greiner Frankfurt Institute for Advanced Studies, Max von Laue Str. 1, 60438 Frankfurt am Main, Germany
The optimized structure and electronic properties of neutral, singly and doubly charged strontium clusters have been investigated using ab initio theoretical methods based on density-functional theory. We have systematically calculated the optimized geometries of those clusters consisting of up to 14 atoms, their average bonding distances, electronic shell closures, binding energies per atom, dissociation energies and the gap between the highest occupied and the lowest unoccupied molecular orbitals [1]. It is demonstrated that the size-evolution of structural and electronic properties of strontium clusters is governed by an interplay of the electronic and geometry shell closures. It is shown that the excessive charge aects the optimized geometry of strontium clusters. Ionization of small strontium clusters results in the alteration of the magic numbers. Stability of positively charged strontium clusters towards ssion is analysed [1],[2]. The obtained results are compared with the available experimental and theoretical data.
(a)
(b)
Figure 1: (a): binding energy per atom for the most stable neutral (lled squares), singly charged (lled circles) and doubly charged (lled triangles) Sr clusters; (b): monomer dissociation energies and ssion barriers for doubly charged strontium clusters. This work is partially supported by the European Commission within the Network of Excellence project EXCELL, and by INTAS under the Grant No. 03-51-6170.
[1]A. Lyalin, I. A. Solovyov , A. V. Solovyov and W. Greiner, submitted to Phys. Rev. A (2007). [2]A. Lyalin, A.V. Solovyov, C. Brchignac, and W. Greiner, J. Phys. B: At. Mol. Opt. Phys., 38, L129 (2005). [3]G.M. Wang, E. Blaisten-Barojas, A.E. Roitberg, and T.P. Martin, J. Chem. Phys. 115, 3640 (2001).
79
A21
POSTERS - SESSION A
Calculations on AuN Cage Structures

Min Zhang York University, Toronto, Canada
Recently, a lot of eort went into the study of the structures of AuN (neutral cluster and anion). There is evidence, from both experiment and theory, that gold clusters possess hollow cage-like structures. Au16 and Au32 appear to have cage structure. In our research, we did global optimization to nd most favored structures for Au16 and Au32 , including neutral clusters and anions. We used plane-wave basis sets and PBE exchange-correlation functional implemented by VASP to evaluate energies. Two optimization algorithms were used in our calculations: 1. Simulated Annealing algorithm supplied by VASP; 2. Tabu Search in Descriptor Space (TSDS) which was developed in our group. According to results obtained so far, the most stable structure for Au16 neutral cluster is at-disc shaped, shown in pictures below. The current energy low-lying structures from our calculations already showed us very interesting structures, some cage-like and others compact. We will calculate the photoelectron spectra for the optimized structures and compare them with the experimental results.
(a)
(b)
Figure 1: (left) Top view of best structure of Au16 neutral cluster. (right) Side view of best structure of Au16 neutral cluster
80
POSTERS - SESSION A
A22
Interplay between Theory and Experiment in Structure Determination of Gas Phase Metal Oxide Clusters
Marek Sierka, Jens Dbler, Joachim Sauer Institut fr Chemie, Humboldt-Universitt zu Berlin, Unter den Linden 6, 10099 Berlin, Germany
The interest in gas phase metal oxides clusters ranges from astrophysics to studies of elementary steps in catalysis. Prerequisite is a detailed knowledge of the atomic structure of the systems, but its determination is a nontrivial task due to a large number of possible congurations. Very often structural models of gas phase clusters are found by intuition, but only in a few simple cases denitive structure assignments have been made. Here we present an approach for fully automatic determination of the atomic structure of gas phase clusters. This hybrid ab initio genetic algorithm (HAGA) is based on a global energy minimization using genetic algorithm in combination with density functional theory [1]. The eciency of the approach is demonstrated for known systems such as gold and boron clusters containing up to 20 atoms. We also study the Al8 O+ ion for which 12 an infrared spectrum by multi-photon dissociation was recently measured [1]. This spectrum shows bands up to 1050 cm1 , which is unusually high for aluminum oxide. Calculated spectra using the structures for Al8 O12 available in the literature are not compatible with the measured spectrum. Global energy minimization using HAGA approach yields a structure that was so far unknown and which does not resemble any of the known solid Al2 O3 phases. Its calculated vibrational spectrum is in excellent agreement with the experimental data. In addition to the cation we have also calculated the global minimum of the neutral Al8 O12 cluster. The structure is distinctively dierent from the cation, showing that the charge can have considerable impact on the structure of gas phase clusters. It is also noteworthy that the structure of the neutral cluster also diers from any of the known solid Al2 O3 phases, so that the a-alumina cluster cutout often employed in theoretical studies does not correspond to the global minimum.
[1]M. Sierka, J. Dbler, J. Sauer, G. Santambrogio, M. Brmmer, L. Wste, E. Janssens, G. Meijer, K. R. Asmis, Angew. Chem. Int. Ed. (2007) in press.
81
A23
POSTERS - SESSION A
Core-Level Photoelectron Spectroscopy on Mass-Selected Lead Clusters at the VUV Free-Electron-Laser FLASH
Volkmar Senz1 , Tim Fischer2 , Patrice Oelner1 , John Neville3 , Markus Scher4 , Jrg Stanzel5 , Heiko Thomas6 , Matthias Neeb5 , Josef Tiggesbumker1 , Michael Martins7 , Eckart Rhl3 , Christoph Bostedt6 , Wolfgang Eberhardt5 , Gerd Gantefr2 , Thomas Mller6 , Horst Schmidt-Bcking4 , Reinhard Drner4 , Wilfried Wurth7 , Karl-Heinz Meiwes-Broer1 1. Insitut fr Physik, Universitt Rostock, Germany 2. Fachbereich Physik, Universitt Kontanz, Germany 3. Physikalische und Theoretische Chemie, Freie Universitt Berlin, Germany 4. Institut fr Kernphysik, Universitt Frankfurt, Germany 5. BESSY Berlin, Germany 6. Institut fr Optik und Atomare Physik, Technische Universitt Berlin, Germany 7. Institut fr Experimentalphysik, Universitt Hamburg, Germany
The electronic structure forms the basis for understanding and tailoring the optical, magnetic and chemical properties of clusters and has therefore attracted a lot of interest. The conrmation of the shell structure of simple metal clusters or the size-dependent chemical reactivity of metal clusters are some of the prominent issues in this eld. Of particular importance is the correlation of the electronic with the geometrical structure, which is hardly accessible by any other experimental technique. A promising method to study this issue is core-level photoelectron spectroscopy of massselected clusters. However, for investigation of the complete valence band and shallow core levels, no photon source except the VUV free-electron-laser FLASH at HASYLAB/DESY is available at the moment. Only this source provides the appropriate radiation of up to 95 eV with sucient high photon ux [1]. First promising results, featuring a size-dependent lead 5d core-level shift, have been obtained during the last year and will be discussed.
[1]V. Ayvazyan et al., Eur. Phys. J. D 37, 297 (2006)
82
POSTERS - SESSION A
A24
Geometric and Electronic Structure of Closed-shell Bimetallic A4 B12 clusters

Yan Sun1 , Rene Fournier2 1. Department of Physics, York University, 4700 Keele Street, Toronto ,ON,M3J1P3 Canada 2. Department of Chemistry, York University, 4700 Keele Street, Toronto ,ON,M3J1P3 Canada
We studied a group of 16-atom metallic clusters having general formula A4 B12 by density functional theory, where A is divalent and B is monovalent. Global optimization [1] was done in each case followed by calculation of energy second derivatives and vibrational frequencies. The clusters have large HOMO-LUMO gaps ranging 1.2 to 2.6eV and other features suggesting special stability. This is consistent with jellium model and 20 electron count. A Td symmetry cage structure is found as the putative global minimum for M g4 Ag12 , M g4 Au12 , Cd4 Au12 and Ca4 N a12 . It is also a low energy isomer for Zn4 Au12, Be4 Au12 and Be4 Ag12 . The Td cage structure has ions arranged in shells, with charge +8 and +12, and the importance of symmetry and ion shells is shown by the relative stability of homotops of M g4 Ag12 .
[1]J.Chen and R. Fournier, Theor. Chem. Acc. 112, 7(2004).
83
A25
POSTERS - SESSION A
Density Functional Study of 13-atom metal Clusters

Yan Sun1 , Rene Fournier2 1. Department of Physics, York University, 4700 Keele Street, Toronto ,ON,M3J1P3 Canada 2. Department of Chemistry, York University, 4700 Keele Street, Toronto ,ON,M3J1P3 Canada
The lowest-energy structures of 4d transition-metal (from Y to Cd) clusters are studied at the size n=13. The global optimization is performed by TSDS (Tabu Search in Descriptor space [1]) with energy evaluated with Gaussian03 and VWN/B3LYP functional. We also studied the energy dierence between our lowest-energy structures and the stable structures previously found such as the buckled biplanar structure [2] and the close-packed icosahedral or cuboctahedral structures.
[1]J. Chen and R. Fournier, Theor. Chem. Acc. 112, 7(2004). [2]C. M. Chang and M. Y. Chou, Phys. Rev. Lett. 93, 133401(2004)
84
POSTERS - SESSION A
A26
Binding energy and preferred adsorption sites of CO on silver-gold cluster cations (Agm Au+ , m+n<7): Kinetic study n and quantum-chemical calculations
Marco Neumaiera , Florian Weigenda , Oliver Hampea,b , and Manfred M. Kappesa,b a Institut fr Nanotechnologie, b Institut fr Physikalische Chemie, Universitt und Forschungszentrum Karlsruhe, D-76128 Karlsruhe, Germany
Room temperature reactivity of carbon monoxide on trapped silver-gold alloy cluster cations (Agm Au+ , n m+n<7) is studied in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer as a function of size and composition. Cluster sizes (m+n)<4 were found unreactive towards CO while the tetramers undergo loss of a neutral a gold or silver atom depending on composition. These reaction channels are in excellent agreement with exothermicities calculated by densitiy-functional theory methods leading to the most stable isomers. Cluster sizes 4<(m+n)<7 adsorb CO and the measured absolute bimolecular rate constants are analyzed by means of a radiative association model (as recently described [1]) to give adsorption energies for the rst CO binding to the alloy cluster cations. These energies are found to decrease strongly with increasing silver content [2] in accord with concomittant quantum-chemical calculations which also predict that CO prefers a gold atom as adsorption site. The general possibility of tuning the adsorption propensities (binding site and energy) of typical -donor molecules to silver-gold nanoalloy clusters is discussed on the basis of molecular orbital theory and contrasted to previous calculations [3].
Figure 1: Binding energies of CO to silver-gold nanoalloy cluster cations (left); relative energies of lowest unoccupied molecular orbitals for penta-atomic Agm Au+ as a function of silver content. n
[1]M. Neumaier, F. Weigend, O. Hampe, and M. M. Kappes, J. Chem. Phys. 122, 104702 (2005); ibid. 123, 04990 (2005). [2]M. Neumaier, F. Weigend, O. Hampe, and M. M. Kappes, J.Chem. Phys. 125, 104308 (2006). [3]V. Bonai-Kouteck, J. Burda, R. Mitri, M. Ge, G. Zampella, and P. Fantucci, J. Chem. Phys. 117, 3120 (2002).
85
A27
POSTERS - SESSION A
Far-infrared spectra of cobalt clusters

Philipp Gruene, Gerard Meijer, Andr Fielicke Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
Metal clusters often exhibit physical and chemical properties that change substantially with cluster size and often dier from those of the bulk phase. One of the important ingredients for understanding this size-dependence is the knowledge of the geometrical and electronic structure of the clusters. Unfortunately, there has been a lack of experimental methods to address this problem. Recently, it has been shown that vibrational spectroscopy in combination with density functional theory calculations can provide information on the geometric structures of free metal clusters containing 3 to more than 20 atoms.[1]-[3] In these studies, the experimental far-infrared spectra of free metal clusters are obtained by multiple photon dissociation (MPD) spectroscopy of their complexes with rare gas atoms. Cobalt clusters are chosen as a topic of investigation since they play an important role in the eld of catalysis, being used for example in the Fischer-Tropsch synthesis, i.e. the catalytic process for obtaining hydrocarbons from CO and H2 . The binding energy of argon to cobalt clusters Co+ is strongly dependent on the cluster size n. Mean surements of the equilibrium constant between the bare metal clusters and their rare-gas complexes as a function of temperature allow for an estimation of the bond dissociation energies (BDE). Values of 0.17 - 0.22 eV are found for n = 3 - 5, while the BDEs for larger clusters are signicantly lower. The high BDEs for Co35 Ar+ make IR-MPD spectroscopy possible even at elevated temperatures of 70 C. Spectra in the range between 100 cm1 and 250 cm1 are presented. At a temperature of -180 C also bigger clusters form metal-rare gas complexes, while in the lower mass regime the mass spectrum is dominated by small cluster complexes containing up to 6 argon atoms. The IR-spectra for each cluster size are unique and clearly distinguishable from each other. With increasing argon coverage the relative absorption cross sections of the complexes increase at the cost of a decreased spectral resolution. The spectral range covered for these systems extends from 80 cm1 to 400 cm1 .
Figure 1: IR-MPD spectra of Co5 Ar+ (n = 1, 4, 5) n
[1]A. Fielicke, A. Kirilyuk, C. Ratsch, et al., Phys. Rev. Let. 93, 023401 (2004). [2]A. Fielicke, C. Ratsch, G. von Helden, et al., J. Chem. Phys. 122, 091105 (2005). [3]A. Fielicke, G. von Helden and G. Meijer, Eur. Phys. J. D. 34, 83 (2005).
86
POSTERS - SESSION A
A28
Spectroscopy on magnesium in superuid helium droplets

Sebastian Gde, Andreas Przystawik, Josef Tiggesbumker, K.-H. Meiwes-Broer Institute of physics, University of Rostock, Universittsplatz 3, 18051 Rostock, Germany
Superuid helium droplets serve for controlled and selective cluster growth and allow spectroscopic measurements near absolute zero temperature, i.e. at 0.4 K [1]. The interaction of the helium environment with a foreign particle is quite sensitive to its electronic properties and might dene the structure of the complex. We have measured the excitation spectra of the 3s3p3s2 transition of Mg atoms solvated in helium nanodroplets with resonant two-photon-ionization under various source conditions. The signal of MgHe50 snowballs are analyzed in order to extract the optical properties. Figure 1 shows the blue shift and line broadening of the atomic absorption line which mirror the recent LIF experiments in nanodroplets and liquids [2], [3]. In [2] the apparent splitting in the spectra was attributed to a quadrupole-like deformation of the cavity around the solute atom after excitation. In contradiction to this model our measurements show that the intensity of the two components strongly correlates with the pick-up density in the scattering cell, indicating that a more complex mechanism is involved. For highly doped droplets the high energy component in the absorption spectra is strongly suppressed whereas for a size distribution with a mean number of one atom per droplet the low energy one is reduced. The latter can be attributed to a resonant excitation of small weakly bound magnesium clusters. The experimental ndings can be explained by a novel formation process of these complexes assisted by the superuid properties of the ultra cold matrix.
Figure 1: Absorption spectrum of the 3s3p3s2 transition of magnesium measured at the MgHe50 ion signal. The spectrum shows two distinct maxima whereas there relative intensities strongly depend on the pick-up density in the scattering cell.
[1]M. Hartmann, R. E. Miller, J. P. Toennies, and A. Vilesov, Phys. Rev. Lett. 75, 1566 (1995). [2]Reho et al., J. Phys. Chem. 104, 3620-3626 (2000). [3]Y. Moriwaki and N. Morita, Eur. Phys. J. D 5, 53-57 (1999)
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A29
POSTERS - SESSION A
Characterization of the Dimerization Eect in Small CrN Clusters by Theoretical Photoabsorption Spectroscopy
J. I. Martnez1,2 , J. A. Alonso1 1. Departamento de Fsica Terica, Atmica y Optica, Universidad de Valladolid, E-47001 Valladolid, Spain 2. Institut fr Theoretische Physik, Freie Universitt Berlin, D-14195 Berlin, Germany
The photoabsorption spectrum of CrN (N = 2-11) clusters have been calculated using time-dependent Density Functional Theory (TDDFT) with a real-space and real-time scheme [1]. Two dierent approximations have been employed for exchange and correlation eects: the adiabatic local density approximation (ALDA) and the self-interaction correction (SIC). The small chromium clusters show peculiarities that make them special compared to clusters of other 3d metals [2], in particular a dimerization eect that controls the initial growth of CrN clusters up to N = 11. This eect is due to the formation of robust closed-shell Cr2 dimers with a strong bond and an unusually short bond length. The calculated spectra in the optical region (0 - 5 eV) for a few representative clusters in this size range are shown in the Figure. The corresponding geometrical structures are also included. The high energy part of the absorption spectra (not shown in the Figure) characterizes the dimerization eect: an excitation peak appears at around 20 eV, and its intensity increases each time a new Cr dimer forms in the structure as the cluster grows. This eect is not tied to any other clustering eect and is only associated to Cr2 .
Figure 1: Calculated photoabsorption cross sections for representative CrN clusters in the range N = 2 - 11.
[1]M. A. L. Marques, A. Castro, G. F. Bertsch and A. Rubio, Comp. Phys. Comm. 151, 60 (2003). [2]J. A. Alonso, Chem. Rev. 100, 637 (2000).
88
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A30
Theoretical Study of Coalescence of Ni nanoparticles

Won Ha Moon, Hee Su Kim, Chul Tack Lim and Chang Hwan Choi Central R & D Institute, Samsung Electro-Mechanics Co., Ltd., Suwon, 443-743 KOREA
The present work investigates the coalescence process of nickel nanoparticles for a host of initial temperatures and starting radii in vacuum with the help of molecular-dynamics (MD) simulations based on the embedded atom potential method [1]. The shell-closed icosahedron nickel nanoparticles could only be preferred until 923 atoms at temperatures no higher than 1380 K, which is in agreement with the experiments. Figure 1 shows the optimized structure of the nickel nanoparticle with 1415 atoms. Figure 2 shows that the structural evolution of Ni nanoparticles during coalescence at 800 K. The melting temperature of larger clusters would depend on their starting structures, which can be attributed to surface premelting. Dependence of total energy per atom and cluster size with dierent atoms on temperature is shown in Fig. 3. With no exception for larger particles, the melting evolution undergoes a surface premelting stage and an overall melting stage before the transformation to liquid phase, and the melting points are signicantly lower than that of bulk Ni. Diverse mechanisms of the rst sintering stage, characterized by a growing neck region, were found.
[1]D. Schebarchov and S. C. Hendy, Phys. Rev. Lett., 95, 116101, (2005).
89
A31
POSTERS - SESSION A
Structures of small noble metal cluster ions

A. Lechtken1 , D. Schooss1 , J. R. Stairs1 , F. Furche2 , O. Kostko3 , N. Morgner3 , B. v. Issendor3 , and M. M. Kappes1,2 1. Institute of Nanotechnology, Forschungszentrum Karlsruhe,D-76021 Karlsruhe, Germany 2. Institut fr Physikalische Chemie, Universitt Karlsruhe, D-76128 Karlsruhe, Germany 3. Fakultt fr Physik, Universitt Freiburg, D-79104 Freiburg, Germany
The structures of small noble metal cluster ions have been studied by the recently developed technique of trapped ion electron diraction (TIED) [1]. The assignment of the structures or the structural motif is done via comparison of the experimental and simulated scattering function, calculated from density functional theory structure calculations. We present a comparison of the structures of Cu , Ag and Au . Our ndings show unambiguously that the structure of Au is predominantly 20 20 20 20 given by a tetrahedron in agreement with the results of Wang et al. [2]. In contrast, structures of Ag and Cu based on the icosahedral motif agree best with the experimental data. The struc20 20 tures of gold clusters ions Au in the size range n = 11-19 have been investigated. While most of n the anionic data is in agreement with structures found before [3], a slightly dierent structure is suggested for Au . 14
Figure 1: The chiral (C3 ) structure of Au (side view left, top view right). The darker atoms are 34 internal atoms Finally the structure of Au34- is presented (see Fig. 1). Based on TIED and photoelectron data a chiral structure with C3 point group symmetry is found in agreement with (time dependent) density functional calculations [4].
[1]M. Maier-Borst, D. B. Cameron, M. Rokni, and J. H. Parks, Physical Review A 59, R3162 (1999), D. Schooss, M.N. Blom, B. v. Issendor, J. H. Parks, and M.M. Kappes, Nano Letters 5, 1972 (2005). [2]J. Li, X. Li, H. J. Zhai, and L. S. Wang, Science 299, 864 (2003). [3]F. Furche, R. Ahlrichs, P. Weis, C. Jacob, S. Gilb, T. Bierweiler, M. M. and Kappes, J. Chem. Phys. 117, 6982 (2002); S. Bulusu, X.Li, L.C.Wang, and X. C. Zeng PNAS, 103, 8326 (2006); X. Xing, B. Yoon, U. Landman, and J. Parks, Phys. Rev. B 74, 165423 (2006); B. Yoon, P. Koskinnen, B. Huber, O. Kostko, B. v. Issendor, H. Hkkinen, M. Mosler, and U. Landman, ChemPhysChem 8, 157 (2007). [4]A. Lechtken, D. Schooss, J. R. Stairs, M. N. Blom, F. Furche, N. Morgner, O. Kostko, B. v. Issendor, and M. M. Kappes, Angew. Chem., Int. Edt. (in press)
90
POSTERS - SESSION A
A32
Structures of small platinum clusters

E. Oger, Th. Bierweiler, P. Weis, M. M. Kappes Institut fr Physikalische Chemie, Universitt Karlsruhe, Germany
The cross sections of small cationic platinum clusters Pt+ (n = 1..9) have been studied using ion n mobility measurements [1]. The clusters are generated by pulsed laser vaporization and mass separated by means of time-ofight (TOF) mass spectrometry. All unwanted ions are removed by a pulsed mass gate. The mass selected clusters are decelerated and injected into a helium lled drift cell. Their cross section is determined by the time it takes for them to drift through the cell guided by a static electrical eld. The clusters are analyzed by a quadrupole mass lter to preclude registration of any fragment ions and detected by a channeltron secondary electron multiplier. To determine the geometry of the clusters, we compare the experimental cross sections with values derived from model structures from ab initio theory (density functional theory (DFT) and Mller-Plesset perturbation theory (MP2)). Three-dimensional structures have been found for platinum clusters as small as n 4 . For comparison cationic clusters of gold, the neighbour in the periodic table of elements, are planar up to n = 7 [2]. In previous work Weis et al. found that the structure of silver cations are planar only for sizes 3 and 4 [3].
[1]Patrick Weis, Stefan Gilb, Philip Gerhardt, and Manfred M. Kappes, Int. J. Mass Spectrom., 216, 59-73 (2002). [2]Stefan Gilb, Patrick Weis, Filipp Furche, Reinhart Ahlrichs, and Manfred M. Kappes, J. Chem. Phys., 116, 4094-4101 (2002). [3]Patrick Weis, Thomas Bierweiler, Stefan Gilb, and Manfred M. Kappes, Chem. Phys. Lett, 355, 355-364 (2002).
91
Methods and Machines
POSTERS - SESSION A
A33
Photon-Trap Spectroscopy for High-Sensitivity Optical Measurements of Trapped Ions and Surface Adsorbates
Akira Terasaki1 , Takuya Majima2 , Kazuhiro Egashira2 , Tamotsu Kondow1 1. Cluster Research Laboratory, Toyota Technological Institute, in East Tokyo Laboratory, Genesis Research Institute, Inc., 717-86 Futamata, Ichikawa, Chiba 272-0001, Japan 2. East Tokyo Laboratory, Genesis Research Institute, Inc., 717-86 Futamata, Ichikawa, Chiba 272-0001, Japan
We present photon-trap spectroscopy developed for high-sensitivity optical absorption and polarization measurements of a trace amount of atoms, molecules, clusters, and their ions in the gas, liquid, and solid phases. The absorption measurement is based on a storage lifetime of photons in a high-nesse optical cavity; the lifetime is free from intensity uctuation of a light source, which limits the sensitivity in conventional transmission spectroscopy. It is operated not only by a pulsed light, known as cavity-ring-down spectroscopy [1], but also by a cw light; the former is described by the time-domain picture with a light pulse traveling back and forth in the cavity, whereas the frequency-domain picture is more appropriate in the latter to deduce a lifetime from the frequency width of the cavity-resonance prole, which enables the analysis even for a cavity containing a solid substrate [2]. The measurement is sensitive to polarization as well [3], allowing studies of magnetooptical phenomena. The photon-trap spectroscopy thus unies all these features of the technique using photons trapped in a cavity. Application to mass-selected trapped ions We have developed an apparatus combining an ion trap with an optical cavity. It is designed so that cross sections of 1016 cm2 (relatively strong electronic transitions) are detectable with 1ppm absorption sensitivity. Mass-selected cluster ions were admitted to a 40-cm linear octopole ion trap, which stored 109 ions and was located in a 1.6-m cavity. Absorption spectra are presented for the manganese ion, Mn+ , in the vicinity of 260 nm, showing 7 P2,3,4 7 S3 transitions with hyperne structures. The measurements were performed under a magnetic eld up to 3 T as well to observe the Zeeman splitting and the Faraday rotation. Cluster experiments are in progress to achieve direct measurements of absorption without using photodissociation/depletion processes. Small manganese cluster ions are to be explored under a magnetic eld to elucidate their ferromagnetism [4]. Application to solids The present technique is applicable to solids, provided that a substrate-form sample with optically at surfaces is placed exactly normal to the cavity axis. Frequency-domain analyses of the properties of this cavity revealed the importance of optical phases in optimizing the signal intensity and the noise level of lifetime measurements [2]. A vibrational spectrum is presented of an alkylsiloxane monolayer adsorbed on a transparent silicon substrate as measured by using a tunable mid-infrared cw light source. It exhibited a clear optical-phase eect; the absorbance was maximized when the monolayer was adjusted at the anti-nodes of a standing wave, while it was practically zero at the nodes. This experimental technique is to be applied to studies of reaction processes of molecules on deposited clusters.
[1]A. [2]A. [3]R. [4]A.
OKeefe and D. A. G. Deacon, Rev. Sci. Instrum. 59, 2544 (1988). Terasaki, T. Kondow, and K. Egashira, J. Opt. Soc. Am. B 22, 675 (2005). Engeln, G. Berden, E. van den Berg, and G. Meijer, J. Chem. Phys. 107, 4458 (1997). Terasaki et al., J. Chem. Phys. 114, 9367 (2001); ibid. 118, 2180 (2003).
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A34
POSTERS - SESSION A
A Novel Method for Measuring Clusters Caloric Curves

Fabien Chirot, Sbastien Zamith, Pierre Labastie, Jean-Marc LHermite Laboratoire Collisions, Agrgats, Ractivit (UMR 5589, CNRS - Universit Paul Sabatier), IRSAMC, 31062 Toulouse Cedex 9, France
Melting of small clusters has received a considerable interest since the pioneer experimental work of Haberland et al who found that the melting temperature of very small particle show a nonmonotonical behaviour. This temperature is found either lower (for the majority of clusters, for instance sodium [1]) or higher (for tin and gallium [2]) than in the bulk. Moreover, both the melting temperature and the latent heat of fusion can vary considerably from one size to another. To our knowledge, only three experimental methods have been used successfully up to now to measure the caloric curve of clusters. In all the experiments, clusters are rst thermalized in a heat bath. In the rst two methods [1], [2] a known temperature shift T is compensated by a known energy shift E in order to observe the same decay rate (i.e. the same internal energy), and then deduce the heat capacity E/T. The energy is brought either by a laser [1] or by collisions [2]. The third method measures the mobility of clusters in a drift tube, from which collision cross sections are deduced. The phase transition from liquid to solid is identied thanks to a variation in the cross section [3]. We propose here a novel method based on an original experimental setup [4] to measure the caloric curve of clusters. The basic idea is to count the number of atoms that can be stuck onto a cluster as a function of its initial temperature. At each sticking, the internal energy of the cluster Mn is increased by a known energy. After a given number of sticking collisions nmax the cluster is so heated that it dissociates before it can stick again. nmax is related to the dissociation time, thus is a measure of the internal energy. As in the rst two experiments mentioned above, we can construct the caloric curve by varying T. Our method does not require laser excitation, is easily transferable to many systems and it is model free. We present here our rst experimental results obtained with sodium clusters. Our results conrm the ones of Haberland et al and extend them towards small sizes.
Figure 1: Comparison of our results (squares) with the one of Haberland et al (circles) [1].
[1]H. Haberland et al, Phys. Rev. Lett. 94, 035701 (2005). [2]G.A. Breaux et al, Phys. Rev. Lett. 91, 215508 (2003). [3]G.A. Breaux et al, J. Phys. Chem. B, 109, 16575 (2005). [4]F. Chirot et al, Rev. Sci. Instrum. 77, 063108 (2006).
96
POSTERS - SESSION A
A35
An experimental setup for uorescence spectroscopy of trapped ions

Mattias Kordel1 , Detlef Schooss1 , Lars Walter1 , and Manfred M. Kappes1,2 1. Institute of Nanotechnology, Forschungszentrum Karlsruhe,D-76021 Karlsruhe, Germany 2. Institut fr Physikalische Chemie, Universitt Karlsruhe, D-76128 Karlsruhe, Germany
We have completed the setup of a new experiment to study the uorescence properties of trapped clusters and nanoparticles in gas phase. Gas phase measurements can help to reveal the dependence of optical properties on size, charge, surface passivation and chemistry. The main advantage of uorescence experiments in gas phase is the total control about environmental eects which otherwise might superimpose the intrinsic qualities of the system under investigation. In contrast to molecular beam methods the trapping of charged particles in a Paul trap allows for a long sampling time, which is critical at low signal levels.
Figure 1: Schematic setup of the TILIF apparatus. Our apparatus comprises an electrospray ionization source (ESI), a quadrupole bender to change the direction of the ion beam, a time of ight mass spectrometer (TOF), and the main chamber with the Paul trap and the optics for inducing and detecting the uorescence. The cluster ions are excited by an Argon Ion Laser perpendicular to the axis of light detection. Resulting uorescence photons are collected in a photon counting photomultiplier tube (PMT), or dispersed using a monochromator/CCD camera. As proof of principle, dispersed uorescence measurements of trapped dye ions (Rhodamine 6G, Rhodamine B, and Rhodamine 101) are presented and compared to solution spectra.
97
A36
POSTERS - SESSION A
Phase, amplitude, and polarization shaped pulses for optimal control on molecules
Fabian Weise, Stefan M. Weber, Mateusz Plewicki and Albrecht Lindinger Institut fr Experimentalphysik, Freie Universitt Berlin, Arnimalle 14, 14195 Berlin, Germany
We present two novel pulse shaper designs, which are capable of manipulating the phase, the amplitude and the polarization of femtosecond laser pulses independently and simultaneously [1] [2]. The capabilities of the polarization modulation with the serial and the parallel setup are demonstrated and the limitations are discussed. Furthermore, we transform the three dimensional electrical eld into the obvious parameters sub pulse energy, position in time, zero order phase, chirps as well as the polarization states ellipticity, major axis angle, and helicity. These parameters are the basis of the shown tailored example pulses, which are retrieved by measuring a set of cross-correlations and spectra [3]. Implementing the serial pulse shaper in a feedback loop raises the level of adaption in coherent control experiments. As a test of this method it is applied on the second harmonic generation. The advantage of manipulating all three parameters of the electrical eld is shown in the optimization of the multi-photon ionization of NaK in a molecular beam. The obtained pulse shape enhances the ionization yield greatly in comparison to traditional optimizations where only the scalar parameters phase and amplitude have been employed. Moreover, the recorded optimized pulseform reveals the particular optimization path via the selected exited states [4].
Figure 1: Serial pulse shaper setup, which is able to shape pulses in phase, amplitude, and polarization. Double pulse with a linear and circular sub-pulse with an amplitude modulation pattern corresponding to the sum-intensity.
[1]M. Plewicki, S. M. Weber, F. Weise, [2]M. Plewicki, F. Weise, S. M. Weber, [3]S. M. Weber, M. Plewicki, F. Weise, [4]F. Weise, S. M. Weber, M. Plewicki,
and and and and
A. A. A. A.
Lindinger, Lindinger, Lindinger, Lindinger,
Appl. Phys. B. 86, 259 (2007). Appl. Opt. 45, 8354 (2006). Phys. Rev. A., submitted Chem. Phys., in press (2007).
98
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A37
New setup for photoelectron spectroscopy of mass selected clusters: high mass range and resolution, high photon energy and high energy resolution
Tim Fischer, Matthias Gtz, Jrn Cordes, Karsten Vetter, and Gerd Gantefr Department of Physics, University of Konstanz, 78457 Konstanz, Germany
New materials for catalysis and hydrogen storage attract more and more attention. For instance, experiments on reactions of gold clusters depict the diverse chemistry for clusters consisting of up to 70-80 atoms [1]. Studies on metal sulde clusters shed light on the underlying mechanisms of their catalytic activity [2]. Furthermore, hydrogen is considered to be one of the most important future energy sources. The main technological problem of a viable hydrogen economy is its storage; clusters may represent a possible answer [3]. To reach the fundamentals of chemistry concerning clusters itself, photoelectron spectroscopy (PES) in the gas phase provides an excellent approach. To get a deeper insight into the clusters the complete conduction band should be investigated [4]. Moreover, bridging the gap towards nanoparticles is still a prospective ambition for cluster research. Investigating adsorbates like hydrogen and oxygen on relatively heavy clusters is only possible, using an intense ion beam and a mass resolution beyond m/m = 1000. In this contribution, we present an improved setup (g. 1) consisting of a pulsed arc cluster ion source, a reectron, an interaction chamber and a F2 -Laser (7.9 eV). Due to the relation m/m = s/s for a time-of-ight spectrometer with reectron the resolution rises with increasing length. Accordingly, the prolongation of the drift length to 12 m enables a higher mass resolution. First results reach a resolution of m/m = 1400 (g. 2). In addition, the interaction chamber was improved to achieve background-free PES measurements even using a F2 -Laser.
Figure 1: (a) New experimental setup: (I) PACIS; (II) TOF tubes; (III) Reectron; (IV) Interaction chamber; (V) F2 Laser Small picture: Improved interaction chamber should allow background-free measurements. (b) Mass spectrum after the improvements. The mass resolution advanced from 400 to 1400.
[1]H.-G. Boyen, G. Kstle, F. Weigl, B. Koslowski, C. Dietrich, P. Ziemann, J. P. Spatz, S. Riethmller, C. Hartmann, M. Mller, G. Schmid, M. G. Garnier, P. Oelhafen, Science 297, 1533 (2002) [2]J. Kibsgaard, J. V. Lauritsen, E. Lgsgaard, B. S. Clausen, H. Topse, and F. Besenbacher, JACS 128, 13950 (2006) [3]Q. Sun, Q. Wang, P. Jena und Y. Kawazoe, JACS 127, 14582 (2005) [4]S. Gemming, J. Tamuliene, G. Seifert, N. Bertram, Y. D. Kim, G. Gantefr, Appl. Phys. A 82, 162 (2005)
99
A38
POSTERS - SESSION A
Metastable Impact Electron Spectroscopy (MIES) of size selected metal clusters

C.J. Harding, V. Teslenko, M. Rttgen, M. Arenz and U. Heiz Lehrstuhl fr Physikalische Chemie 1, Technische Universitt Mnchen, Lichtenbergstr. 4, D-85748 Garching, Germany
The formation of a beam of helium metastable atoms can be used as an extremely sensitive and non-destructive probe of surfaces and concomitant adsorbates. This type of spectroscopy (MIES) is performed through the detection of energy resolved electrons released through Auger-like processes caused by the interaction of the metastables with surface based systems. MIES was used, in parallel with FTIR and pulsed molecular beam methods (p-MBRS) to probe model catalysts. The model catalysts were made by depositing mass selected and mass distributed Pd or Au clusters onto thin lms of MgO. Firstly, MIES was used to characterise the MgO substrate. Following this, the detection limit was tested using various mass distributed gold cluster coverages. Finally, MIES was used to investigate the presence of an oxide intermediate in CO oxidation reactions involving mass selected Pd13 clusters, in parallel with other surface based techniques.
100
POSTERS - SESSION A
A39
Strong Field Excitation of Metal Clusters and Fullerenes with EUV Free Electron Laser Pulses
Johannes Passig1 , Tilo Dppner1 , Paul Radclie2 , Volkmar Senz1 , Slawomir Skruszewicz1 , Hubertus Wabnitz2 , Josef Tiggesbumker1 and Karl-Heinz Meiwes-Broer1 1. Institut fr Physik, Universitt Rostock, Universittsplatz 3,18051 Rostock, Germany 2. HASYLAB at DESY, Notkestrasse 85, 22607 Hamburg, Germany
We describe in detail an experimental system which has been designed to study the strong eld interaction of extreme ultra-violet (EUV) light with nanoparticles at the free electron laser facility FLASH (DESY, Hamburg). In addition to the direct photoionization of the atoms, the high intensity of the FEL pulses may lead to cooperative eects in the ionization process, e.g. eld-assisted ionization and enhancement by many body eects [1],[2]. Here we present rst results of time-ofight experiments on ions emitted by lead clusters and fullerenes exposed to the EUV-FEL pulses at a fundamental wavelength of 32 nm (38.5 eV). For lead, the spectra exhibit a broadening and splitting of the ion signal indicating a Coulomb explosion of the clusters. The results for C60 show signals of highly charged fullerenes and carbon fragments.
Figure 1: Time-of-ight-spectrum of lead ions and small clusters emitted by lead nanoparticles (N2000) exposed to intense EUV laser light. The spectrum is averaged over 2000 FEL pulses. Singly charged fragments of the particles can be detected up to N=8. No atomic ions with charge states larger than two can be identied. The signals of Pb+ and Pb++ show a clear splitting indicating Coulomb explosion of the particles.
[1]U. Saalmann and J.M. Rost, Phys. Rev. Lett. 89, 143401 (2002). [2]T. Dppner et al., Phys. Rev. Lett. 94, 013401 (2005).
101
A40
POSTERS - SESSION A
High Yield Cluster Source Combining Magnetron Sputtering and Aggregation Techniques
Juri Demuth, Ewald Janssens, Shaohui Li, Torsten Siebert, Ludger Wste Institut fr Experimentalphysik, Freie Universitt Berlin, Arnimallee 14, 14195 Berlin, Germany
High particle density is generally favorable for optical spectroscopy of clusters. In order to meet this requirement, a cluster source combining magnetron sputtering and gas aggregation has been constructed for the application in femtosecond time-resolved NeNePo (negative ion-to-neutral-topositive ion) spectroscopy with a design inspired by previous work [1],[2]. The advantage of this cluster source in comparison with alternative methods such as laser vaporization and electrospray is a high and continuous yield of ionized clusters in the size range of interest (n = 1-10). Generally, the method of magnetron sputtering is an advanced sputtering technique, which is prevalent in thin lm production. The ionization of the sputtered clusters takes place through sputtered secondary electrons, which are forced on spiral trajectories by a magnetic eld. Inside a liquid nitrogen cooled and helium lled chamber, cluster growth takes place through three-particle- and cluster-clustercollisions. The general design of the constructed magnetron sputter source is presented in this work, together with a discussion of various parameters such as voltage and discharge currency of the sputter source, Argon / Helium - partial pressure, temperature and nozzle size of the aggregation chamber for attaining clusters with the desired attributes. Furthermore, the application of this source to the study of nuclear dynamics in silver oxides and the controlled optical preparation of reactive structures by means of femtosecond time-resolved NeNePo will be discussed [3].
Figure 1: Design drawing of the constructed magnetron sputter source. Part A Torus sputter source; Part B source mount; Part 1 ange with feedthrough for liquid nitrogen, Helium and Argon; Part 2 vacuum chamber; Part 4 cooled aggregation chamber; Part 6 front plate with nozzle at the end of the aggregation zone.
[1]H. Haberland, M. Karrais, M. Mall, Z.Phys.D 20, 413-415 (1991). [2]S. Pratontep, S.J. Carroll, C. Xirouchaki, M. Streun R.E. Palmer, Rev. Sci. Instrum. 76, 045103 (2005). [3]T. Leisner, S. Vajda, S. Wolf, L. Wste, J. Chem. Phys., 111, 1017-1019 (1999).
102
POSTERS - SESSION A
A41
Structure of Medium-Sized Sodium Clusters

Oleg Kostko1 , Bernd Huber2,3 , Michael Moseler2,3 , Bernd von Issendor1 1. Fakultt fr Physik, Universitt Freiburg, Hermann-Herder-Strae 3, 79104 Freiburg, Germany 2. Fraunhofer Institut fr Werkstomechanik, Whlerstrae 11, 79108 Freiburg, Germany 3. Freiburg Materials Research Center, Stefan-Meier-Strasse 21, 79104 Freiburg, Germany
The properties of nanoparticles and clusters are dominated by electronic and geometric nite size effects, that is by the discretization of the electronic density of states and the surface induced tendency towards nonbulklike crystalline structures. Therefore, the knowledge of electronic and geometrical structures of the clusters is the basis for an understanding of more complex eects in small particles. But the information about structures in the intermediate size range (1-10 nm) is scarce. For sodium clusters, there exists some information about small clusters, obtained from photoelectron spectroscopy and DFT calculations [1], and about large clusters, obtained from mass spectrometry [2]. Here, by a combined photoemission and density functional theory study we are assigning for the rst time building principles of medium-sized sodium clusters. The growth pattern of all clusters studied here favor icosahedron-based geometry. Surprisingly, the assigned geometrical structures of small (20<N<60) sodium cluster anions follow quite well jellium model predictions, as is evident from a calculation of the clusters radii of inertia. In this respect the electronically magic clusters Na and Na are close to perfectly spherical, whereas 39 57 intermediate clusters exhibit a change of geometrical shape from prolate (which appears immediately after electronic magic number) to oblate (appearing closer to the next electronic magic number). Bigger sodium clusters between complete Mackay icosahedra (Na , Na , and Na ) are formed 55 147 309 by addition of twisted Mackay overlayers as predicted by Murrell-Mottram potential calculations [3], leading to prominent subshell closings at sizes 71, 92, 178, 206, and 216 [4].
[1]M. Moseler, B. Huber, H. Hkkinen, U. Landman, G. Wrigge, M. Astruc Homan, B.v. Issendor, Phys. Rev. B 68, 165413 (2003). [2]T.P. Martin, T. Bergmann, H. Ghlich, T. Lange, Z. Phys. D 19, 25 (1991). [3]E.G. Noya, J.P.K. Doye, D.J. Wales, arXiv :cond-mat/0506329. [4]O. Kostko, B. Huber, M. Moseler, B.v. Issendor, Phys. Rev. Lett. 98, 043401 (2007).
103
A42
POSTERS - SESSION A
Molecular Dynamics for Fission Processes

O. I. Obolensky, A. Lyalin, I. A. Solovyov, A. Yakubovich, E. Henriques, A. V. Solovyov, W. Greiner Frankfurt Institute for Advanced Studies, Max-von-Laue-Str. 1, 60438 Frankfurt am Main, Germany
Fission is a ubiquitous process playing important roles in many physical phenomena. In ssion, the initial and nal states of a system are separated by a potential barrier, the so-called ssion barrier. The height and the shape of this barrier determine most of the experimental observables of the process, such as characteristic ssion times and branching ratios between dierent ssion channels. We discuss relative advantages and disadvantages of two general approaches which are used for carrying out a molecular dynamics analysis of ssion processes [1]. The goal of both approaches consists in nding the optimum ssion pathway which minimizes the ssion barrier. The optimum ssion pathway frequently involves complicated rearrangements of the ionic structure including formation of intermediate metastable congurations [2] which makes this problem rather dicult. The rst approach to the molecular dynamics analysis is the conventional molecular dynamics simulations which emulate the evolution of a system with time [3],[4]. This approach relies on the assumption that the system explores suciently large volumes of its phase space (thus covering suciently large areas of the potential energy surface) if a suciently large number of runs of the simulations are made and each run is suciently long. In order to shorten the required CPU time one usually assigns rather high initial temperatures to the system. In such a case, however, the system tends to ssion along the shortest path rather than along the path with the lowest potential barrier. Therefore, one has to nd the optimum balance between the reliability and the feasibility of simulations. The second approach consists in a direct (manually- or algorithmically-driven) exploration of the potential energy surface of the system [5]. This approach allows one to perform a systematic analysis of the various ssion scenarios, reducing the chance of an accidental omission of an important ssion pathway. We review one of the possible algorithms for exploration of the potential energy surface [2],[5] and give examples of its applications to ssion processes in atomic clusters, bio- and macromolecules. We acknowledge partial nancial support from INTAS (contract 03-51-6170) and from European Commission (project EXCELL).
[1]A. Lyalin, O.I. Obolensky, A.V. Solovyov, W. Greiner, Int. J. Mod. Phys. E, 15, 153 (2006) [2]O.I. Obolensky, A.G. Lyalin, A.V. Solovyov, W. Greiner, Physical Review B, 72, 085433 (2005) and references therein [3]P.-G. Reinhard and E. Suraud, Introduction to Cluster Dynamics (Wiley-VCH, Weinheim, 2004). [4]F. Baletto and R. Ferrando, Rev. Mod. Phys., 77, 371 (2005) [5]O.I. Obolensky, I.A. Solovyov, A.V. Solovyov, W. Greiner, Computing Letters, 1, 313 (2005)
104
POSTERS - SESSION A
A43
Noble Metal Cluster Reaction Kinetics in a New Ion Trap Reectron ToF-Mass Spectrometer Setup
Sandra M. Lang, Thorsten M. Bernhardt 1. Insitut fr Oberchenchemie und Katalyse, Universitt Ulm, 89069 Ulm, Germany
About two decades ago the fascinating and unexpected catalytic properties of supported clusters of gold and silver have been discovered. In the meantime it was shown that not only dispersed gold nanoparticles deposited on oxide supports but also small gold particles in the gas phase exhibit catalytic properties in the CO oxidation reaction. However, the reaction mechanism and the development of catalytic cycles is not always understood in detail. For a detailed study of the mechanism of molecular processes as well as the inuence of dierent parameters as the charge state and the size of the cluster, humidity, and temperature isolated clusters in the gas phase represent an ideal model system. So far the clusters are produced by an ion sputtering source (CORDIS), transferred and thermalized by a helium lled quadrupole and mass selected by a further quadrupole. The clusters are then transferred to an octopole ion trap, which can be cooled down to 40K. Here the cluster beam is in contact with reactive gases. The reaction products are then analyzed in a last quadrupole mass spectrometer. For a fast and high resolution detection of the reaction products an additional time-of-ight mass spectrometer was recently inserted. The combination of an octopole ion trap and a quadrupole mass analyzer with the new time-of-ight mass spectrometer is discussed in detail. Furthermore, the setup of a new magnetron cluster source to obtain clusters with up to 4000 amu is shown.
105
A44
POSTERS - SESSION A
Conguration interaction for large scale vibrational calculations

David Benoit and Yohann Scribano Theory Group -SFB 569, University of Ulm Albert-Einstein-Allee 11, Ulm, D-89081 Germany
The computation of the thermal properties of nanosystems (e.g. heat conduction) or the simulation of infrared spectra of polyatomic molecules both require an accurate theoretical description of the vibrational excited states of the system. However, the most widespread theoretical method for the prediction of vibrational frequencies - the harmonic approximation - is not able to accurately reproduce the dynamics of polyatomic molecules far from their equilibrium geometry. In our approach, we use a direct vibrational self-consistent eld (VSCF) scheme to obtain the vibrational wave function. This scheme is also able to treat larger molecular systems for which exact theoretical methods cannot be used. We present a description of vibrational excited states based on a conguration-interaction (VCI) approach within the VSCF technique. We also introduce a new approach that reduces the computational cost of VCI calculations for excited states of large systems and examine the convergence behaviour of VCI-based methods for molecular systems such as H2 O, NH3 , CH4 and HF on graphite.
106
Molecular Clusters
POSTERS - SESSION A
A45
Evidence for mode specic fragmentation in the infrared spectrum of NH+ (H2 O) 4
Anita Lagutschenkov1 , Tobias Pankewitz1 , Sotiris S. Xantheas2 , Yuan-Tseh Lee3 , Gereon Niedner-Schatteburg1 1. Physikalische Chemie, Technische Universitt Kaiserslautern, Erwin-Schrdinger-Strae, 67663 Kaiserslautern, Germany 2. Chemical Science Division, Pacic Northwest National Laboratory, 902 Battelle Boulevard, P.O. Box 999, MS K1-83, Richland, Washington 99352, USA 3. Institute of Atomic and Molecular Science, Academia Sinica, P.O. Box 23-166, Taipei, Taiwan 106, Republic of China
We present the gas phase infrared (IR) spectrum of the singly hydrated ammonium ion, NH+ (H2 O) 4 in the spectral region from 3250 to 3810 cm1 [1]. The spectrum was recorded by photofragmentation of isolated, mass selected ions. The experimental results are interpreted using high level ab initio calculations, including anharmonic calculations of vibrational spectra. The four bands obtained are assigned to N-H and O-H stretching modes. The recorded relative band intensities compare favorably with the predictions of ab initio calculations - except for the 3 (H2 O) band, where the experimentally observed value is about 20 times weaker than calculated. A similar behavior has previously been reported for several action spectra of other hydrated cations, in which the 3 (H2 O)/1 (H2 O) intensity ratios become smaller the stronger the complexes are bound. The recorded ratios vary, in particular among the data collected from action spectra that were recorded with and without rare gas tagging [2]-[5]. Inspection of calculated anharmonic coupling constants in NH+ (H2 O) reveals that the coupling of 4 the 3 (H2 O) mode to other cluster modes is indeed weaker than that of the 1 (H2 O) mode by orders of magnitude. This leads to a mode specic fragmentation dynamic in the action spectra of NH+ (H2 O) in particular and of most monohydrated cations in general. 4
[1]T. Pankewitz, A. Lagutschenkov, S. S. Xantheas, Y.-T. Lee and G. Niedner-Schatteburg, J. Chem. Phys. accepted. [2]T. D. Vaden, C. J. Weinheimer and J. M. Lisy, J. Chem. Phys. 121 (7), 3102 (2004). [3]J. H. Choi, K. T. Kuwata, B. M. Haas, Y. B. Cao, M. S. Johnson and M. Okumura, J. Chem. Phys. 100 (10), 7153 (1994). [4]C. J. Weinheimer and J. M. Lisy, J. Chem. Phys. 105 (7), 2938 (1996). [5]N. Solca and O. Dopfer, J. Phys. Chem. A. 107 (20), 4046 (2003).
109
A46
POSTERS - SESSION A
Microsolvation of NaSO and MgNO+ in water clusters 4 3

Barbara Jagoda-Cwiklik Institute of Organic Chemistry and Biochemistry Academy of Sciences of the Czech Republic and Center for Biomolecules and Complex Molecular Systems Flemingovo n. 2, Prague,16610, Czech Republic
This study presents results of our investigation of microhydration of sodium sulfate and magnesium nitrate molecular ions. Up till now, there exist studies concerning microsolvation of atomic ions and their ion pairs. In this work we focus on complex ions pairs and their hydration. In particular, we are interested in the process of conversion of contact ion pairs (CIP) to solvent separated ion pairs (SSIP). We aim at getting a microscopic picture of interactions of water molecules with ion pairs and the mechanism of their separation, especially to answer the question how many water molecules are needed to separate the investigated CIPs. To explore and to understand how water interacts with NaSO and MgNO+ we used ab initio MP2 4 3 calculations (or DFT method for the biggest clusters) with aug-cc-pvDZ basis sets and we compared our results with available experimental data. In case of sodium sulfate anion, according to our calculations, the rst water molecule is located aside of NaSO ion-pair. It binds both to the sodium cation and oxygen atom in SO . The second 4 4 and the third water behave in a similar way, each forms one hydrogen bond with one sulfate oxygen atom and interacts with Na+ . In cluster with 3 water molecules water forms a solvation ring between sodium cation and sulfate anion and this ring begins to separate the cation from anion. Calculated vertical detachment energies are in good agreement with experimental ones. Clusters containing up to 15 water molecules were also studied and in the system with 13 solvent molecules we eventually found SSIP. In the studies of MgNO+ ion pair, we located a new energeticaly optimal structure of the 5-water 3 cluster where one of water molecules is located in the second solvation shell. An addition of sixth water molecule causes that the solvent separated ion pair is formed where the magnesium cation is surrounded by six water molecules and the nitrate anion is located in second solvation shell.
110
POSTERS - SESSION A
A47
Structure of Coronene Clusters

O. I. Obolensky, A. V. Solovyov, W. Greiner Frankfurt Institute for Advanced Studies, Max-von-Laue-Str. 1, 60438 Frankfurt am Main, Germany
Clusters of polycyclic aromatic hydrocarbons (PAH) and their ions are believed to be one of the most probable species in the interstellar space responsible for converting the UV radiation of the stars into the intensive IR radiation, known as unidentied infrared bands [1], [2]. The current knowledge of structure and properties of PAH clusters is very limited. Laboratory studies have just started to appear while reliability of the theoretical results is limited due to the subtle interplay between the van der Waals polarization forces and the electrostatic interaction [3].
We have recently performed density functional theory (DFT) calculations of energies for four plausible congurations of dimer of coronene (C2 4H1 2) [3] (shown on the left). The stack congurations (superimposed stack (SS), twisted stack (TS) and parallel-displaced (PD) stack) are favoured by the van der Waals forces while the T-shaped conguration is favoured by the electrostatic interaction. In order to get a better description of the van der Waals interaction, the DFT results were corrected by a phenomenological London-type 1/r6 term. Depending on the magnitude of this term, both the T-shaped and the PD stack congurations can be the global minimum conguration of the system. It is quite surprising that the T-shaped conguration is energetically competitive for such a large system for which a graphite-like stacked structure had been a priori expected. On the basis of the DFT calculations we developed a model in which each coronene molecule is represented by a set of four charged rings [3]. Adjusting the parameters of these rings both the T-shaped and the stack congurations can be made energetically preferable congurations. We found the global energy minimum structures of the coronene clusters in the situation when the electrostatic interaction dominates and in the situation when the van der Waals forces prevail (also studied previously [4]). Rotational constants and the normal modes in the obtained sets of structures are distinctively dierent making possible to distinguish experimentally between the two situations. We acknowledge partial nancial support from the European Commission (project EXCELL).
[1]W. W. Duley, S. Lazarev, Astrophysical Journal, 612, L33 (2004) [2]M. Rapicioli, C. Joblin, P. Boissel, Astronomy and Astrophysics, 429, 193 (2005) [3]O. I. Obolensky, V. Semenikhina, A. V. Solovyov, W. Greiner, in print (available on-line), Int. J. of Quantum Chemistry (2007) [4]M. Rapacioli, F. Calvo, F. Spiegelman, C. Joblin, D. Wales, J. Phys. Chem. A, 109, 2487 (2005)
111
Phase Transitions
POSTERS - SESSION A
A48
Supersonic Jets at High Stagnation Pressures: Cooling, Nucleation, Thermodynamics

Wolfgang Christen, Tim Krause, Sibylle Rabeus, Klaus Rademann Institut fr Chemie, Humboldt-Universitt zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany
Motivated by the possibility to study molecular behavior at very low temperatures the interest in cold molecules has grown enormously in recent years [1]. Among the various techniques approaching the unexplored millikelvin regime are supersonic beams, providing, most notably, superuid helium droplets [2]. While an increase in stagnation pressure of the gas increases the number of collisions taking place during expansion and thus signicantly enhances the cooling eciency of supersonic jets, condensation and cluster formation is considered as a limiting factor [3]. Surprisingly, at high stagnation pressures the inuence of thermodynamic parameters on the relative molecular velocities in supersonic beams is virtually unexplored. At such conditions new, more complex phenomena due to the presence of phase transitions must be taken into account. Therefore we have investigated pulsed, supersonic jet expansions of neat CO and CO2 at high stagnation pressures by time-of-ight measurements. In fact, unprecedented low translational temperatures have been observed, if the molecules are expanded from their supercritical state [4]. The remarkably low translational temperatures of less than 100 mK are rationalized by the large heat capacity in the vicinity of the critical point, allowing condensation and cluster formation without signicant increase in temperature.
[1]Special Issues on Cold Molecules, Eur. Phys. J. D 31 (2004), J. Phys. B 39 (2006). [2]J. P. Toennies, A. F. Vilesov, Annu. Rev. Phys. Chem. 49, 1 (1998). F. Stienkemeier, K. K. Lehmann, J. Phys. B 39, R127 (2006). [3]M. Hillenkamp, S. Keinan, U. Even, J. Chem. Phys. 118, 8699 (2003). [4]W. Christen, K. Rademann, U. Even, J. Chem. Phys. 125, 174307 (2006).
115
A49
POSTERS - SESSION A
Experimental characterization of nucleation center formation and growth sequence in the clustering of unsupported nanoparticles
P. Feiden, J. Leygnier, Ph. Cahuzac, C. Brchignac Laboratoire Aim Cotton, C.N.R.S. UPR 3321, Bt. 505 Universit Paris Sud, F91405 Orsay Cedex, France
The condensation of a nano droplet in a supersaturating vapor decomposes in two steps: the formation of a nucleation center, also called critical nuclei or nucleation seed, and the growth sequence, by accretion of further atoms on the nucleation center. These two steps were investigated separately through the clustering of homogeneous Nan and Heterogeneous Nan X particles in a helium buer gas, with X = (NaOH)2 or (Na2 O)2 . Heterogeneous Nan X clusters are formed by the growth sequence of atoms sticking on X molecules diusing in a supersaturing vapor of sodium. The mean number of atoms condensed on the nucleation center increases with the sodium concentration. For growth sequence, the temperature of helium buer gas is essential. When the helium gas is cold enough, it prevents nascent clusters from evaporation and all the cluster-atom collisions are sticking ones, leading to large clusters. Turning the buer gas to a higher temperature modies the balance between atom accretion and cluster evaporation, and thus the mean cluster size of the distribution decreases. The cluster size distribution against sodium concentration and Helium temperature is well interpreted by a monte carlo simulation assuming growth by sequential accretion of atoms with hard sphere cross section and an energy dissipation function of the buer gas temperature.
Figure 1: Time of Flight mass spectra for Nan and Nan (NaOH)2 clusters produced without (trace a) and with (trace b) injection of preformed (NaOH)2 molecules in a supersaturating sodium vapor.
116
Rare Gas Clusters
POSTERS - SESSION A
A50
Multiply charged neon cluster ions: critical size and Coulomb explosion
I. Mhr1 , F. Zappa1 , S. Deni1 , D. Kubala2 , O. Echt3 , T. D. Mrk1,2 and P. Scheier1 1. Institut fr Ionenphysik und Angewandte Physik, Leopold Franzens Universitt Innsbruck, Technikerstr. 25, A-6020 Innsbruck, Austria. 2. Department of Experimental Physics, Comenius University, SK-84248 Bratislava, Slovak Republic 3. Department of Physics, University of New Hampshire, Durham, NH 03824, USA
Multiply charged neon cluster ions are formed upon electron impact ionization of large neutral clusters and analyzed utilizing a two sector eld mass spectrometer applying techniques developed recently [1]-[3]. The critical size for doubly charged neon cluster ions is determined experimentally with isotopically pure 20 Ne to be 287. In spectra of natural neon, the presence of doubly charged clusters can be observed as an increase of the ion yield at the same cluster size conrming the above result. This method allows in addition an approximate determination of the critical sizes for triply charged cluster ions. Utilizing a beam deection method [4] it is possible to observe (for the rst time) directly the asymmetric ssion of multiply charged neon clusters right after the ionization event. The most abundant low mass fragment ion from this reaction process is the dimer ion. The yield of larger fragment ions decreases exponentially with the fragment size. The kinetic energy of the emitted low mass fragment ions is of the order of 200 meV which is surprisingly low when comparing the results with a simple point charge model taking into account the critical cluster sizes presently determined.
Figure 1: Part of a mass spectrum for a Nen cluster beam consisting of isotopically pure
20
Ne.
This work was supported in part by the FWF, Wien and the European Commission, Brussels. F.Z. acknowledges gratefully support by the Brazilian agency CNPq.
[1]I. Mhr et al., Phys. Rev. Lett. 98 (2007) 023401. [2]S. Deni et al., J. Chem. Phys. 124 (2006) 054320. [3]S. Feil et al., Int. J. Mass Spectrom. 252 (2006) 166. [4]S. Feil et al., Int. J. Mass Spectrom. 233 (2004) 325.
119
A51
POSTERS - SESSION A
Appearance Sizes of Multiply-Charged Van der Waals Clusters

Masato Nakamura1 , Paul-Antoine Hervieux2 1. College of Science & Tech, Nihon University, Narashinodai, Funabashi, 274-8501, Japan 2. Institut de Physique et Chimie des Materiaux de Strasbourg, UMR 7504 ULP-CNRS, 23 Rue du Loess, BP 43, F-67034 Strasbourg, France
Multiply-charged clusters are stable if the energy barrier exists for every ssion channel. About 20 years ago, Echt et al. [1] calculated the energy barrier using the liquid drop model with an assumption that the two fragment clusters are in contact at the transition state (the so-called contact sphere model) and estimated the appearance sizes for multiply-charged Van der Waals clusters. Their calculations well explained the experimental measurements on the appearance sizes of many multiply-charged clusters. However, some discrepancies still exist for some clusters such as that of Ar. Very recently, the appearance sizes of doubly- and triply- charged Ne clusters have been measured [2]. The appearance sizes are found to be much smaller than those estimated by the model described in [1]. To reveal these discrepancies, we recalculate the appearance size of multiplycharged Van der Waals clusters. In [1], the parameters for the liquid drop model were those given by Brian and Burton (BB) [3]. Recently, some groups [4] have calculated the energy of global minimum of Lenard-Jones clusters up to size n = 1000. We nd that the liquid drop energy using the BBs parameters, deviates largely from the value obtained in [4] if n exceeds 100. Thus, we propose a new set of parameters which reproduces these recent calculations. Using this new expression, we calculate the appearance sizes of Van der Waals clusters. Some of them are listed in Table I. As for Ar clusters, our predictions are in better agreement with the experimental measurements. For Ne clusters, the discrepancy is diminished although it is still insucient to explain the new experimental ndings. We also study the role of the geometrical shell eects on the stability of multiply-charged Van der Waals clusters. In some cases, it is plausible that the appearance size varies due to shell eects [5]. Detailed report will be given elsewhere [6].
Figure 1: Appearance Sizes of Multiply-Charged Van der Waals Clusters.
[1]O. Echt et al., Phys. Rev. A 38, 3236 (1988). [2]I. Maehr et al., Phys. Rev. Lett. 98, 023401 (2007). [3]C. L. Briant and J. J. Burton, J. Chem. Phys. 63, 2045 (1975). [4]D. Wales and J. Doye, J. Phys. Chem. A 101, 5111 (1997), Y. Xiang et al., J. Phys. Chem. A, 108, 3586 (2004). [5]M. Nakamura and P.-A. Hervieux, Chem. Phys. Lett. 428, 138 (2006). [6]M. Nakamura and P.-A. Hervieux, Preparation for publication
120
POSTERS - SESSION A
A52
Stable Structures of the Small and Medium-Size Singly Ionized Helium Clusters.
Daniel Hrivk, Karel Oleksy, Ren Kalus, Frantiek Karlick Department of Physics, University of Ostrava, 30. dubna 22, Ostrava, 701 03, Czech Republic
The semiempirical triatomics-in-molecules (TRIM) method has been applied to study singly ionized helium clusters. Stable structures for the clusters of sizes 3 20 have been found through the use of the special optimization method based on the genetic algorithm. A comparison with results obtained by the method of conjugated gradients has been done. The basic principle of the TRIM method as well as an overview about He+ potential energy surfaces used is presented. 3
121
Posters - Session B
Carbon and Silicon
POSTERS - SESSION B
B1
Phase Transitions in Fullerenes

Adilah Hussien, Ilia A. Solovyov, Andrey V. Solovyov and Walter Greiner Frankfurt Institute for Advanced Studies, Johann Wolfgang Goethe University, Max-von-Laue Str.1, Frankfurt am Main, Germany Email: hussein@as.uni-frankfurt.de
We investigate the various fragmentation and formation channels of fullerenes using a statistical description rst applied to polypeptide folding [1]. In this formalism, the growth and fragmentation of fullerenes are treated as phase transitions, and we present a scheme of constructing a parameterfree partition function describing such a process. Thus, we develop a theory describing all essential thermodynamical properties such as heat capacity, free energy and the phase transition temperature. The predictions of our theory are compared with available experimental measurements on the melting of fullerenes [2] and with results from molecular dynamics simulations [3]. Two examples of possible fragmentation channels of C60 are shown in Figure 1. Channel (a) corresponds to the transition of C60 in the gas phase of 30 C2 molecules, while channel (b) corresponds to the polymerization of the fullerene.
Figure 1: Possible fragmentation channels of C60 into a gas or polymer phase
[1]A. V. Yakubovich, I. A. Solovyov, A. V. Solovyov and W. Greiner, Eur. Phys. J. D (Highlight paper) 40, 363 (2006); Europhysics News, in print (2007) [2]Y. Jin, J. Cheng, M. Varma-Nai, G. Liang, Y. Fu, B. Wunderlich, X. Xiang, R. Mostovoy and A. Zetti, J. Phys. Chem. 96, 5151 (1992) [3]S. G. Kim and D. Tom?nek, Phys. Rev. Lett. 72, 2418 (1994)
127
B2
POSTERS - SESSION B
Deuteration of solid fullerene lms versus the structure of Cn cages

D. Ler, S.-S. Jester, P. Weis, A. Bttcher, M. M. Kappes Lehrstuhl fr die Physikalische Chemie Mikroskopischer Systeme, Institut fr Physikalische Chemie, Universitt Karlsruhe (TH), D-76128 Karlsruhe, Germany
The deuteration of solid fullerene lms has been investigated by means of thermal desorption spectroscopy, TDS, quadrupole mass spectrometry, ultraviolet photioionization spectroscopy, UPS, and atomic force microscopy, AFM. We compare here the monodisperse lms consisting of small nonIPR carbon cages, Cn 50 n 58, with the classical IPR fullerenes as represented by C60 . The lms have been created under ultra high vacuum conditions by depositing low-energy mass-selected C+ ions onto HOPG [1]. The stability of the non-IPR Cn lms is governed by pairs of adjacent n pentagons in Cn cages, 2AP, which are responsible for the formation of covalently stabilized [Cn ]m oligomers [1]-[3]. In contrast, C60 lms as molecular crystals are stabilized by weak van der Waals interactions. Mass spectra of particles sublimating from deuterated C58 lms reveal broad distributions of C58 Dn cages with recognizable maxima at n=6, 26 and 30. Thermal decomposition of such lms is marked by considerably lower sublimation temperatures than that found for bare C58 lms. The progressing deuteration process manifests itself also by a gradual lowering of the work function (down to 3.6 eV) and a signicant increase of the ionization potential (up to 7.2 eV for C58 Dn cages). AFM images of deuterated lms reveal a thermally induced transition from dendritic islands of C58 oligomers into smooth-rim islands composed of deuterated cages. This transition results from a gradual replacement of the 2AP-2AP bonds by deuterium atoms tied at cage periphery what leads to the formation of molecular solid stabilized by only weakly interacting C58 Dx cages [4]. In contrast to non-IPR lms (Cn , 50 n 58) the deuteration of C60 lms raises the binding energy of adjacent cages. The initial deuteration stages are associated with the formation of polymeric chains likely comprising covalently interlinked cages which exhibit higher thermal stability than pristine C60 lms. The corresponding sublimation heat increases with the deuterium dose applied and levels o at a value of 2.15 eV/cage. For comparison, the higher deuterofullerenes, C60 D36 , exhibit sublimation energy of 1.39 eV/cage, considerably lower than the polymeric chains but comparable to pristine C60 lms. The polymer-based capping layers are air resistant and amenable to fabricate stable multi layered [C60 /C60 Dx ]m lms [5]. The evident dierence in the deuteration routes found here for the IPR and non-IPR fullerene classes can be assigned to the structure-specic reaction centers terminating the non-IPR cages.
[1]A. [2]A. [3]D. [4]D. [5]D.
Bttcher, P. Weis, A. Bihlmeier, M.M. Kappes, PCCP 6 (2004) 5213 Bttcher, P. Weis, S.-S. Jester, D. Ler, A. Bihlmeier, W. Klopper, M.M. Kappes, PCCP, 7 (2005) 2816 Ler, S. S. Jester, P. Weis, A. Bttcher and M. M. Kappes, J. Chem. Phys. 124 (2005) 054705 Ler, S. S. Jester, P. Weis, A. Bttcher and M. M. Kappes, J. Chem. Phys. 125 (2006) 224705 Ler, P. Weis, A. Bttcher and M. M. Kappes, J. Phys. Chem. , submitted, 2007
128
POSTERS - SESSION B
B3
Modeling Carbon Nanotube Double-Layer Capacitors

Lars Pastewka1 , Michael Moseler1,2 1. Fraunhofer Institut fr Werkstomechanik, Whlerstrae 11, 79108 Freiburg, Germany 2. Freiburger Materialforschungszentrum, Stefan-Meier-Strae 21, 79104 Freiburg, Germany
Capacitors with capacities of several Farads, sometimes termed "Supercaps", have been in scientic focus for some time now. In this context, carbon nanotubes (CNTs) have been proposed for use as an electrode material for electric double-layer capacitors (EDLC). The advantage of CNTs is the large surface area exposed to the electrolyte and their inertness with respect to chemical reactions [1]. Except for a few experimental [2] and theoretical [3] studies on gated CNTs not much is known about the detailed capacitive response of these systems. For CNTs immersed in an electrolyte as used in EDLCs the microscopic mechanisms are still unclear [4]. Here, we present a large scale study on the capacitive response of CNTs immersed in an electrolyte. Our study is based on density-functional based tight-binding at the self-consistent charge level of theory [5]. In our calculations, the electrolyte is included within a mean-eld approach. This is achieved by smearing out the double-layer charges on an idealized cylinder. All calculations are performed with full relaxation of the atomic positions because part of the stored energy is of elastic origin. For a water based electrolyte, the quantum and classical contributions to the capacity are similar in magnitude. We also nd that the total dierential capacity per double-layer surface does strongly depend on the charging level, or bias potential, of the nanotube and increases with increasing tube diameter. The capacities for dierent tubes in a charge neutral environment are given in gure 1.
Figure 1: Dierential capacity per double-layer surface as a function of tube radius for a water based electrolyte. Labels give the chirality of the respective CNT. The 10x10-5x5 tube is double-walled with a 10x10 outer and a 5x5 inner wall.
[1]D. S. Futaba et al., Nat. Mat. 5, 987 (2006); B.-J. Yoon et al., Chem. Phys. Lett. 388, 170 (2004); K. H. An et al., Adv. Mat. 13, 497 (2001) [2]S. Ilani et al., Nat. Phys. 2, 687 (2006) [3]L. Latessa et al., Phys. Rev. B 72, 035455 (2005); P. Pomorski et al., Phys. Rev. B 69, 115418 (2004); P. Pomorski et al., Phys. Rev. B 67, 161404 (2003); J. Luo et al., Phys. Rev. B 66, 115415 (2002) [4]I. Heller et al., J. Am. Soc. Chem. 128, 7353 (2006) [5]See: P. Koskinen, H. Hkkinen, G. Seifert, S. Sanna, Th. Frauenheim and M. Moseler, New J. Phys. 8, 9 (2006) and references therein.
129
B4
POSTERS - SESSION B
Chirality of Single Walled Carbon Nanotubes and its Inuence on the Energetics and Stability
Maneesh Mathew, Ilia A. Solovyov, Andrey V. Solovyov and Walter Greiner Frankfurt Institute for Advanced Studies, Johann Wolfgang Goethe University Max-von-Laue-Str. 1, 60438, Frankfurt am Main, Germany E-mail:mathew@as.uni-frankfurt.de
We systematically study carbon nanotubes of various chiralities and their stabilities to understand how the chirality inuences the binding energy of nanotubes. Both ab initio and molecular mechanics methods are used for the investigation. The ab initio density functional theory (DFT) calculations are performed with the use of Gaussian 03 software package [1] and the molecular mechanics calculations are performed with the use of NAMD software package [2]. The results obtained through these studies are used for a better understanding of the growth mechanism of carbon nanotubes [3], [4]. The mechanism which controls the growth of a nanotube of desired chirality is poorly understood. Our studies can be used for the theoretical investigation of the dependence of growth of carbon nanotube on its chirality. The following gure explains the concept of the chirality of a nanotube by depicting how a nanotube of certain chirality, characterized by two integer numbers n and m, can be constructed from a graphite sheet. The gure below shows the structure of a chiral nanotube, corresponding to n=7 and m=4, being a typical conductive nanotube.
Figure 1: : (a) Chirality vector shown in a graphite sheet; (b) The nanotube formed after folding the graphite sheet in gure-(a) along the chirality vector. This work was supported in part by INTAS (project No 03-51-6170), by EU through the EXCELL project and by EU through PECU project.
[1]Gaussian 03, Revision C.02, M. J. Frisch, et al, Gaussian, Inc., Wallingford CT (2004) [2]J.C. Phillips, et al, J. of Comp. Chem., 26, 1781 (2005) [3]Feng Ding, Kim Bolton and Arne Rosen, J. Phys. Chem. B 108, 17369 (2004) [4]J. Gavillet, et al, Phys. Rev. Lett., 87, 27 (2001)
130
POSTERS - SESSION B
B5
Photoelectron spectroscopy of fullerene dianions C2 (86 n n 98)

K. Matheis, O. T. Ehrler, M. M. Kappes Institut fr Physikalische Chemie, Universitt Karlsruhe (TH), Germany
Several doubly negatively charged fullerenes were examined with laser photoelectron spectroscopy at photon energies of 2.33, 3.49, 4.66, and 6.42 eV [1]. By determining the vertical detachment energies and their dependence upon the cage size, the range of experimentally determined electron anities of the higher homologous of the carbon clusters was extended [2],[3]. Furthermore repulsive Coulomb barriers have been extracted from the spectra and discussed in consideration of the existing 2 results on smaller fullerenes and in terms of an electrostatic model. For the 19 IPR-isomers of C86 semiempirical calculations of the second electron anities have been made. Gas phase dianions were generated by electrospray ionization from a fullerene solution in o-dichlorobenzene containing TDAE as an electron donor [4]. After leaving the heated desolvation capillary, the ions were transmitted through an electrodynamic ion funnel and accumulated in a hexapole ion trap for 33 ms interface the cw ion source to a pulsed reectron time-of-ight mass spectrometer. After passing the reectron, mass selected fullerene dianions were decelerated before entering the detachment region of a magnetic bottle photoelectron spectrometer. Here they were irradiated with higher harmonics of the Nd:YAG or the fundamental wavelength of an ArF-laser. Arrival time distributions of the emitted electrons was measured and converted to energy spectra. The obtained data of the second electron anities are in good agreement with results from a classical electrostatic model, although this was compiled for spherical objects. Calculations considering ellipsoidal deformations show that dierences in the potential energies are negligible with respect to the resolution of our experimental setup. The repulsive Coulomb barrier heights are in agreement with predictions from electrostatic theory.
[1]K. [2]O. [3]O. [4]O.
Matheis, O. T. Ehrler and M. M. Kappes, in preparation T. Ehrler, J. M. Weber, F. Furche, and M. M. Kappes, Phys. Rev. Lett. 91, 113006 (2003). T. Ehrler, J. M. Weber, F. Furche, and M. M. Kappes, J. Chem. Phys. 122, 094321 (2005). Hampe, M. Neumaier, M. N. Blom, and M.M. Kappes, Chem. Phys. Lett. 354, 303 (2002).
131
B6
POSTERS - SESSION B
Kinetic Model for Nanotubes Growth

O. I. Obolensky, I. A. Solovyov, A. V. Solovyov, W. Greiner Frankfurt Institute for Advanced Studies, Max-von-Laue-Str. 1, 60438 Frankfurt am Main, Germany
Size selected nanoclusters of such metals as Ni, Fe, Co are widely used as catalysts in the chemical vapor deposition (CVD) techniques of production of carbon nanotubes [1]. The characteristics of the nanotubes as well as the parameters of their growth are closely related to the size and properties of the catalytic particles [1]. Despite of intensive studies the physical mechanism responsible for the catalytic action of the nanoclusters leading to the nanotubes growth is not yet known.
We have developed a kinetic model describing the process of catalytically assisted growth of carbon nanotubes. The model describes the ow of carbon atoms starting from the catalytic decomposition of the feedstock molecules at the surface of the nanocluster and ending at their embedding into the nanotube. In the gure we show a cross section of the nanocluster and the nanotube with the schematic representation of the carbon ows which are accounted for by the model. Feedstock molecules are decomposed on the catalytically active part of the nanocluster surface, which is exposed to the environment and not screened by any additional inactive layers (region "c"). The carbon atoms from this region diuse (either along the surface or through the bulk of the cluster) into the other parts of the cluster. We single out the growth region from which the atoms embed themselves into the nanotube walls (region "g") and the near-surface region inside the nanotube (region "b"). From the region "b" carbon atoms can reach the growth region by surface or bulk diusion or they can evaporate. Some of the evaporated atoms are deposited on the nanotube walls and reach the growth region by surface diusion. We also account for the possibility of decomposition of the feedstock molecules directly by the nanotube walls. Thus, we present a model comprehensively describing the kinetics of the nanotube growth. The model allows one to predict with a reasonable accuracy the distribution of carbon within the catalytic nanoparticle, the relative importance of various growth mechanisms, the nanotube growth rate, etc. However, the results are rather sensitive to the input parameters (e.g., diusion coecients, activation energies for embedding into the nanotube) which are to be obtained from accurate quantum mechanical calculations or experiments. We acknowledge partial nancial support from the European Commission (project EXCELL).
[1]M. Chhowalla et al., J. Appl. Phys., 90, 5308 (2001) and references therein.
132
POSTERS - SESSION B
B7
UV-vis and IR multi-photon electron detachment spectroscopy of C2 76

O. Hampe1,4 , M. Neumaier1 , Bruno Concina1,5 A.D. Boese1 , J. Lemaire2 , P. Matre2 , G. Niedner-Schatteburg3 , and M. M. Kappes1,4 1 Institut fr Nanotechnologie, Forschungszentrum Karlsruhe, 76021 Karlsruhe, Germany; 2 Laboratoire de Chimie Physique (CNRS-UMR-8000), Universit Paris XI, Orsay Cedex 91405, France; 3 Fachbereich Chemie, Technische Universitt Kaiserslautern, 67663 Kaiserslautern, Germany; 4 Institut fr Physikalische Chemie, Universitt Karlsruhe, 76128 Karlsruhe, Germany; 5 present address: Laboratoire de Spectromtrie Ionique et Molculaire, CNRS and Universit Lyon I, 69622 Villeurbanne cedex, France.
Doubly negatively charged C2 may serve as a model system of a molecular multianion for inves76 tigating the electron-electron interaction ("Coulomb barrier") as well as the eect of the excess charges on the molecular structure (electron-lattice interaction). We present results from two spec2 troscopic probes on electrosprayed C76 using two experimental ion trap setups: 2 (i) Laser-photoexcitation of C76 and C2 in the Uv-vis region (using 2nd and 3rd harmonics of a 84 ns-pulsed Nd:YAG laser coupled to the Karlsruhe FT-ICR mass spectrometer) is studied in detail at dierent wavelengths as a function of laser uence to give information on the degree of internal excitation required to induce electron loss on the experimental time scale and the mechanism of electron emission (statistical vs. direct detachment). Electron loss response is modelled by thermionic emission kinetics leading to an eective Coulomb barrier height. [1] (ii) IR vibrational spectra of C2 (as the rst gas-phase IR spectrum of an isolated multianion) 76 are obtained at the free-electron laser facility CLIO on a ESI-Q-trap mass-spectrometer setup. The spectrum is contrasted to computed harmonic vibrational frequencies based on density-functional theory. They show that the excess charges lead to a fairly small distortion of the fullerene cage which maintains its D2 symmetry prevailing for neutral C76 .
Figure 1: left: Fluence dependence (data points, at 355 nm) of electron loss eciency modelled with a one and two-photon absorption law; inset: thermionic emission lifetime after one-photon absorption bracketing an eective Coulomb barrier (exp. time scale as horizontal lines); right: FELIR-multi-photon detachment spectrum of C2 (solid line) contrasted to DFT computations employing 76 two dierent functionals/basis sets shown as stick plots.
[1]B. Concina, M. Neumaier, O. Hampe, M. M. Kappes, Int. J. Mass Spectrom. 252, 110 (2006). [2]M. Neumaier, A.D. Boese, J. Lemaire, P. Matre, G. Niedner-Schatteburg, M. M. Kappes, and O. Hampe, in prep. (2007).
133
B8
POSTERS - SESSION B
Screening of a Conned Atom by a Fullerene of Finite Thickness

S. Lo1 , , A.V. Korol1,2 and A.V. Solovyov1 1. Frankfurt Institute of Advanced Studies, Johann Wolfgang Goethe-Universitt, Max-von-Laue-Str. 1, 60438 Frankfurt am Main, Germany 2. Department of Physics, St. Petersburg State Maritime Technical University, Leninskii prospect 101, St. Petersburg 198262, Russia Email: lo@as.uni-frankfurt.de
An atom conned within a fullerene is dynamically screened from the external electromagnetic eld - it experiences a eld that is amplied - leading to an enhancement of the photoabsorption of the conned atom. The amplication occurs in a certain frequency range determined by the plasmon excitation in the conning fullerene. This enhancement factor was discussed by Connerade and Solovyov in [1] for the case of the innitely thin fullerene. The dynamical enhancement factor due to a fullerene of nite thickness is presented here. The existence of a second surface of this fullerene is signicant as this allows for the presence of two surface plasmon modes [2], in contrast to the single plasmon considered in [1]. The gure is a plot of the enhancement factor for the innitely thin fullerene and the fullerene of nite thickness. The prole of the enhancement factor for the thick fullerene has an additional feature, which is due to the manifestation of the second plasmon mode, as indicated by the arrow in the gure.
Figure 1: A plot comparing the enhancement factor of the innitely thin fullerene and the fullerene of nite thickness. This work was supported in part by INTAS (project number 03-51-6170) and by EU through the EXCELL project.
[1]J.-P. Connerade and A.V. Solovyov, J. Phys. B: At. Mol. Opt. Phys., 38, 807 (2005) [2]A.V. Korol and A.V. Solovyov, Phys. Rev. Lett. (to be published in 2007)
134
Clusters and Hydrogen
POSTERS - SESSION B
B9
Optical Excitations in CdS Nanoparticles

Johannes Frenzel, Jan-Ole Joswig, and Gotthard Seifert Physikalische Chemie, Technische Universitt Dresden, Bergstr. 66b, D-01062 Dresden, Germany
The absorption spectra of cadmium sulde nanoparticles with up to 2000 atoms have been calculated using a density-functional tight-binding method and linear-response theory. We have considered dierent stoichiometries, underlying crystal structures (zincblende, wurtzite, rocksalt), and particle shapes (spherical, cuboctahedral, tetrahedral). Moreover we have investigated the inuence of saturation with hydrogen atoms on the spectra. Saturated particles show a decreasing lowest excitation energy with increasing particle size due to the quantum-connement eect. Dangling bonds at unsaturated surface atoms introduce trapped surface states which lie below the lowest excitations of the completely saturated particles and, thus, close the gap between highest occupied and lowest unoccupied molecular orbital. Moreover, we nd strong excitonic onset excitations arising from the molecular orbitals close to the Fermi level. These orbitals show the shape of the angular momenta of a hydrogen atom (s, p). Some of these excitations have a collective character. Zincblende- and wurtzite-derived particles show very similar spectra, whereas the spectra of rocksaltderived particles are rather featureless. Particle shapes that conne the orbital wavefunctions strongly (tetrahedron) give rise to less pronounced spectra with lower oscillator strengths. The agreement of our data with experimentally available spectra and excitation energies is very good.
137
B10
POSTERS - SESSION B
Chemical Reactivity of Small Palladium Clusters with H2 and O2 in a Cluster Beam Experiment
Mats Andersson and Arne Rosn Department of Physics, Gteborg University, SE-41296 Gteborg, Sweden
The reactivity of neutral palladium clusters towards diatomic molecules such as O2 and H2 was investigated in a cluster beam experiment. A beam of clusters seeded in He gas is generated in a pulsed laser-vaporisation source. After expansion the beam passes a skimmer and then two collision cells, in which a low pressure of a reactive gas can be maintained. The clusters, with or without adsorbed molecules, are detected with laser ionisation and time-of-ight mass spectrometry. By measuring the number of molecules adsorbed on the clusters as a function of pressure in the collision cells, the reaction probability in a cluster-molecule collision can be determined using a pseudo-rstorder kinetic model [1]. The reaction probability of the Pdn with O2 molecules was investigated for cluster sizes up to n=28. The formation of Pdn O2 products was observed for sizes from n=5, and Pdn O4 products from about n=15. The reaction probability with the rst O2 molecule is around 0.5-0.7 for sizes n=10-28, and the size-to-size variations are limited. For the smallest sizes the measured reaction probability is lower. The observation of threshold sizes and a lower reactivity of the smaller sizes is thought to be an eect of insucient stability of the reaction products for clusters having only few vibrational degrees of freedom to accommodate the chemisorption energy [1]. The reaction probability of O2 on palladium clusters has a similar value as on nickel clusters [2], but it is slightly lower than for cobalt [1] and rhodium [3] clusters, and higher than for platinum clusters [4]. When the Pd clusters react with O2 in the rst collision cell and H2 (D2 ) in the second cell, there is evidence of reactions between oxygen and hydrogen on the clusters. If the O2 pressure is kept constant and the H2 pressure is successively increased, it is observed that the number of adsorbed oxygen atoms is decreasing. This behavior is similar to what was observed for O2 and D2 adsorption on platinum clusters [4]. The loss of oxygen atoms can be explained by formation of water molecules that subsequently desorb from the clusters.
[1]M. [2]M. [3]M. [4]M.
Andersson, J.L. Persson and A. Rosn, J. Phys. Chem., 100, 12222 (1996). Andersson, L. Holmgren, J.L. Persson, T. klint, and A. Rosn, Mat. Res. Soc. Symp. Proc., 351, 299 (1994). Andersson, L. Holmgren, and A. Rosn, Surf. Rev. Lett., 3, 683 (1996). Andersson and A. Rosn, J. Chem. Phys., 117, 7051 (2002).
138
POSTERS - SESSION B
B11
Hydrogen Sorption Characteristics of Boron, Carbon and/or Nitrogen-Based Materials Decorated by Transition Metal Clusters
Nobuyuki Nishimiya Department of Materials Science, Toyohashi University of Technology, Tempaku-cho 1-1, Toyohashi 441-8580, Japan
Nano-structured carbonaceous materials and B-C-N compounds (BN, CN and BCN) were comparatively prepared and characterized in order to discover novel materials with high hydrogen capacity. Nano-structured carbonaceous materials decorated by Pd or 3d transition metals such as Ti, V, Cr, Fe, Co etc. possessed limited hydrogen capacity of 0.1-0.4 wt.% at 298 K under 100 kPa of hydrogen, which was lower than the maximum hydrogen concentration, 0.86 wt.% [1], in single walled carbon nanotubes containing both Y and Ni. The hydrogen capacity positively correlates with surface area as illustrated in Figure 1, where data are plotted for 3d transition metals. The straight line is drawn so as to have a slope of 0.303 wt.%/200 m2 g1 , which is essentially the same as reported for nanocarbons at 77 K [2]. The capacity was also governed by content of carbon and strength of graphitic G band of Raman spectrum. The eect of decoration with metals is qualitatively interpreted by stability of hydrogen in assumed C2 M2 tetrahedron evaluated by quantum mechanical calculation, DV-X. Decoration of BN, CN and BCN with Pd again enhanced hydrogen capacity, but maximum hydrogen concentrations were as low as 0.1 wt.% at 298 K and 100 kPa. Decorated BCN had the largest hydrogen capacity, but lost the decoration eect on repeated sorption and desorption of hydrogen. Decorated BN showed reversed behavior. While specic surface area of BN (before decoration) increased through heat treatments, hydrogen capacity did not monotonously increase with specic surface area. It is to be resolved how starting BN powders are reproducibly prepared with surface area and porosity regulated.
Figure 1: Variation of hydrogen capacity at 298 K and 100 kPa with surface area.
[1]N. Nishimiya, K. Ishigaki, H. Takikawa, M. Ikeda, Y. Hibi, T. Sakakibara, A. Matsumoto and K. Tsutsumi, J. Alloys and Comp. 339, 275-282 (2002). [2]A. Zttel, P. Sudan, Ph. Mauron, T. Kiyobayashi, Ch. Emmenegger and L. Schlapbach, Int. J. Hydrogen Energy 27, 203-212 (2002).
139
B12
POSTERS - SESSION B
Hydrogen peroxide and ammonia on protonated ice clusters

Martin Schmidt1 , Albert Masson1 and Catherine Brchignac1 , Hai-Ping Cheng2 1. Laboratoire Aim Cotton, CNRS, Bt 505, Universit Paris sud, 91405 Orsay Cedex, France Martin.Schmidt@lac.u-psud.fr 2. Department of Physics & QTP, University of Florida Gainesville, FL 32611, USA
A temperature-controlled source for protonated water clusters has been combined with high-resolution mass spectroscopy to study the stability pattern of ice-clusters and compounds with ammonia and hydrogen peroxide depending on temperature. The stability pattern of pure protonated ice shows the two well-known peaks at 21 and 28 molecules and also less pronounced structure up to n = 55. Ammonia and hydrogen peroxide do not destroy this pattern but shift it by a number of water molecules. The additives are therefore integrated in the persisting crystalline structure of the pure protonated ice. Based on this structural information, DFT calculations reveal that hydrogen peroxide and ammonia occupy surface positions on a dodecahedral 21-molecule cluster and are not caged in the center.
140
POSTERS - SESSION B
B13
Hydrogen Induced Transition From Dissociative to Molecular Chemisorption of CO on Vanadium Clusters

Ingmar Swart1 , Andr Fielicke2 , Britta Redlich3 , Gerard Meijer2 , Bert Weckhuysen1 and Frank de Groot1 1. Department of Chemistry, Utrecht University, Sorbonnelaan 16, 3584 CA Utrecht, The Netherlands 2. Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195, Berlin, Germany 3. FOM Institute for Plasmaphysics, Edisonbaan 14, 3439 MN, Nieuwegein, The Netherlands
Transition metal nanoparticles play an important role in catalysis and hydrogen storage materials [1]. The presence of adsorbates on nanoparticles can strongly inuence their properties with respect to these applications. Transition metal clusters, on which molecules are adsorbed, are useful model systems to study the fundamental aspects of the metal-adsorbate interaction. Here we present results on the determination of the structure of hydrogen covered transition metal complexes and on the eect of co-adsorption of H2 and CO. Vibrational spectroscopy is applied to obtain structural information on the binding geometries of H2 and CO on cationic vanadium clusters in the gas-phase. Experimental IR spectra of cluster complexes have been obtained via InfraRed Multiple Photon Dissociation (IR-MPD) spectroscopy [2] using the Free Electron Laser for Infrared experiments (FELIX) as an intense and tunable light source in the 300-2200 cm 1 spectral range. The experimental spectra are augmented with density functional calculations to obtain the ground state geometries of the cluster complexes as well as the corresponding IR spectra. We report on the size-dependent interaction of carbon monoxide molecules with hydrogen covered vanadium clusters containing between 5 and 20 metal atoms. It is shown that hydrogen is predominantly adsorbed in three fold hollow sites with a minor number of hydrogen atoms adsorbed in bridging sites. The CO molecule dissociates on bare vanadium clusters, in agreement with CO adsorption on bulk vanadium [3]. Co-adsorption of H2 leads to molecular binding of CO on the metal clusters as evidenced by the presence of a (CO) stretching band in the infrared spectra. We show that dissociative chemisorption is prevented when the potential binding sites of atomic C and O atoms are blocked by H atoms [4].
[1]A.T. Bell, Science, 299, 1688 (2003). [2]A. Fielicke, G. Meijer, G. von Helden, J. Am. Chem. Soc. 125, 3659 (2003). [3]G. Broden, T.N. Rhodin, C. Brucker, Surf. Sci. 59, 593 (1976). [4]I. Swart, A. Fielicke, B. Redlich, G. Meijer, B.M. Weckhuysen, F.M.F. de Groot, J. Am. Chem. Soc. in press (2007).
141
B14
POSTERS - SESSION B
Controlling the Activation of CO Adsorbed on Cobalt Clusters by Co-adsorption of H2

Ingmar Swart1 , Andr Fielicke2 , David M. Rayner3 , Bert Weckhuysen1 , Gerard Meijer2 and Frank de Groot1 1. Department of Chemistry, Utrecht University, Sorbonnelaan 16, 3584 CA Utrecht, The Netherlands 2. Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195, Berlin, Germany 3. Steacie Institute for Molecular Sciences, National Research Council, 100 Sussex Drive Ottawa, Ontario, K1A 0R6, Canada
Reactions of small molecules with transition metal nanoparticles have attracted considerable interest over the past decades since they can provide a conceptual framework for applications such as heterogeneous catalysis and hydrogen storage. Especially the reaction of H2 and CO with Fe and Co has been widely studied due to the relevance to the Fischer-Tropsch process in which a mixture of H2 and CO is converted into long chain hydrocarbons. Here we report on the co-adsorption of H2 and CO on small cationic Co clusters (Co+ , n=4-20) in n the gas-phase, specically addressing the eect on the C-O bond. Vibrational spectroscopy is used to monitor the C-O bond strength, relying on InfraRed Multiple Photon Dissociation (IR-MPD) spectroscopy [1] to measure the IR spectra of (hydrogenated) mono-carbonyl complexes in the range of the C-O stretch vibration (1600 - 2200 cm1 ). The presence of a C-O stretch band in the 1950 2100 cm1 spectral range indicates that CO is exclusively linearly coordinated to bare and hydrogen covered cationic cobalt clusters. Upon increasing H2 coverage, the C-O stretch frequency shifts to higher energy. To explain and quantify the observed eect, we extended a recently developed model [2] that describes the size and charge dependence of the C-O stretch vibration of a CO molecule bound to late transition metal clusters to incorporate the co-adsorption of hydrogen. We show that by forming Co-H bonds, hydrogen controls the electron density available for back-donation to the CO. On average each adsorbed H atom formally withdraws 0.09-0.25 electrons, depending on the size of the cluster [3].
[1]A. Fielicke, G. Meijer, G. von Helden, J. Am. Chem. Soc. 125, 3659 (2003). [2]A. Fielicke, G. von Helden, G. Meijer, D. B. Pedersen, B. Simard, D. M. Rayner, J. Chem. Phys. 124, 194305 (2006). [3]I. Swart, A. Fielicke, D.M. Rayner, G. Meijer, B.M. Weckhuysen, F.M.F. de Groot, submitted for publication
142
Deposited Clusters
POSTERS - SESSION B
B15
Production and Nanolithography on Silicon Cluster Films

B. Rasul, S. Jaksch, F. Zappa, P. Scheier Institut fr Ionenphysik und Angewandte Physik, Leopold-Franzens-Universitt Innsbruck, Technikerstrasse 25, A-6020 Innsbruck, sterreich
Films of silicon clusters are formed by magnetron sputtering and deposited onto freshly cleaved highly oriented pyrolitic graphite (HOPG) surfaces. The topography of the lms and the growth behavior as a function of the sputtering parameter are analyzed with a variable temperature scanning tunneling microscope (STM). This instrument enables to investigate the silicon clusters in a temperature range from 25K to approximately 1300K. The electronic properties of the lms are probed by local scanning tunneling spectroscopy. The sample preparation chamber is connected via an ultra high vacuum gate directly to the STM chamber which reduces oxidation and passivation of the silicon clusters to a minimum. In the present study, we analyze the dependence on the distance between the HOPG surface and the magnetron, the argon gas pressure, the discharge current, and also the deposition time. The distance has the strongest inuence on the sputtering behavior. The Ar pressure aects both the growth rate of the lms and the sticking coecient of the silicon clusters on the HOPG. For high pressure we observe an increased mobility of the clusters. Furthermore, the overall roughness of the lm increases with higher pressure. Very low pressure (0.4 Pa) results in fractal structures and decoration of defects in the HOPG substrate. Well dened manipulation in the nanometer regime of the lms with the STM tip is demonstrated with dierent techniques. At increased bias-voltage, applied between the tip and the silicon cluster lm, we are able to fuse silicon nanoparticles into larger objects. Thereby the electronic density of states is strongly increased and probed with complementary scanning tunneling spectroscopy measurements. At increased tunneling current silicon clusters can be gently vaporized which results in regions with reduced roughness. Finally at low bias voltages the silicon clusters can be wiped away with the tip. Surprisingly this extreme procedure generally does not aect the quality of the tip and high resolution images of the manipulated sample can be taken with the same tip. It is planned to determine the conditions for a lm that has optimum properties for subsequent nanolithography as described above. A high resolution grey scale image will be imprinted on such a lm. The stability of freshly formed lms and also the imprinted nanolithography is studied at elevated temperatures in the STM.
145
B16
POSTERS - SESSION B
Electronic excitations induced by the impact of coinage metal ions and clusters on a rare gas matrix: neutralization and luminescence
Christoph Sieber1 , Wolfgang Harbich1 , Karl-Heinz Meiwes-Broer2 and Christian Flix1 1. Institut de Physique des Nanostructures, Ecole Polytechnique Fdrale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland 2. Fachbereich Physik, Universitt Rostock, D-18051Rostock, Germany
Rare gas matrices are model systems in solid state physics. They are used to provide softlanding conditions to size-selected clusters impinging on a surface because they are inert and relatively soft. Classical molecular dynamics calculations have been used to describe and understand the nuclear mechanics of the deposition process, however much less studies have focused on electronic processes. Here we show that collisions of atomic ions and cluster ions with rare gas covered metal substrates lead to light emission which is element and size specic (g.1). In these low energy ion substrate collisions, it is not the direct energy transfer into the electronic system of the cluster, but the creation of an exciton, which is trapped in the rare gas layer, that carries the excitation energy. We propose a model for the excitation mechanism that explains the observed luminescence as well as the neutralization of the clusters in the rare matrix. Strong links with thermoluminescence and other thermostimulated processes are found.
Figure 1: (a) Spectrally resolved luminescence of Ag+ , Ag+ and Ag+ and (b) of Au+ , Au+ during 1 2 3 1 2 the deposition in an argon matrix.
[1]C. Sieber, W. Harbich, K.-H. Meiwes-Broer, & C. Flix, Chem. Phys. Lett.,433, 32-36 (2006)
146
POSTERS - SESSION B
B17
Absorption spectroscopy of size-selected neutral gold clusters in argon matrices

V. Rodrigues1,2 , F. Conus1 , A. Rydlo1 , S. Lecoultre1 and C. Flix1 1. Institut de Physique des Nanostructures, Ecole Polytechnique Fdrale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland 2. Instituto de Fsica "Gleb Wataghin," UNICAMP, C.P.6165, 13083-970 Campinas SP, Brazil.
The interest for gold clusters has been renewed both for fundamental reasons as well as for potential applications. Dierent calculations of low energy structure show that for small gold clusters, the relativistic eects result in an increased stability of the planar structures that are the most stable structures for small clusters in the gas phase. From the point of view of applications, recent studies have shown their potential for catalysis as well as their interesting optical properties. Only very few reports on theoretical and experimental investigations of the optical properties of gold clusters exist, this being probably related to their absorption cross section that is an order of magnitude smaller than for silver. Here we report new absorption spectra of gold Au17 nanoclusters. Because of the lower cross section, these measurements required the use of a device recently developed in our group [1] that has an increased optical path and therefore sensitivity. The spectra are compared to the available experimental and theoretical data. A rst analysis of the spectra is performed using the Mie formalism by introducing explicitly the lowest energy structures resulting from the reported calculations. Despite the simplicity of this model, this analysis yields surprisingly good results for the clusters that have a structure with symmetry compatible with an ellipsoid.
[1]Conus, F.; Lau, J.T.; Rodrigues, V. & Flix, C. Rev. Sci. Instrum., 77, 113103 (2006).
147
B18
POSTERS - SESSION B
Oxidation/Reduction of Aun (n=2-13) clusters on SiO2 /Si and HOPG

Rainer Dietsche1 , Dong Chan Lim1 , Moritz Bubek1 , Thorsten Ketterer1 , Karsten Vetter1 , Young Dok Kim2 , and Gerd Gantefr1 1. Department of Physics, University of Konstanz, Universittsstrasse 10, 78457 Konstanz, Germany 2. Division of Nano Sciences and Department of Chemistry, Ewha Womans University, Seodaemoon-gu, Daehyun-dong 11-1, 120-750 Seoul, Korea
Au nanoparticles show enhanced catalytic activity in contrast to bulk Au, which is chemically inert [1]. One of the central questions for these Au nanoparticles is the origin of this activity. Possible reasons are the electronic structure due to the conned electrons or geometric eects like undercoordinated atoms. The metal-oxygen interaction may also be important. Results for small Au clusters on metal-oxide surfaces show that chemical properties can change drastically with each additional atom [2]. In our experiment small mass-selected Au cluster anions were softlanded on various substrates. Oxidation and Reduction behavior was studied by X-Ray Photoelectron Spectroscopy (XPS). On Si wafers covered with native oxide layers mass-selected Aun (n=2-13) cluster anions were deposited. In order to increase defect density the wafers were etched before introducing to the UHV system. Regarding the appearance of Au-oxide peaks the results indicate an interesting even-odd pattern in oxidation behavior for n=4-8 as it has previously been found for Au anions in gas phase experiments [3]. Because of their low reactivity towards atomic oxygen Au5 and Au7 can therefore be suggested to be highly stable. The oxidized clusters can be reduced by CO. Exposure of these clusters to NaOH solution leads to an inversion of the observed even-odd alternation.
Figure 1: Au4f XPS spectra of Aun clusters on SiO2 /Si after exposure to oxygen atmosphere. For Aun (n=2-9) clusters on sputtered HOPG this even-odd pattern in chemical properties is not observed. However, Au8 seems to exhibit a more readily uptake of atomic oxygen compared to the other clusters. Again the oxidized Au8 cluster can be reduced by CO. STM measurements of Au7 clusters show that this cluster is stable on defects and exhibits two layer, 3D structures.
[1]R. Meyer et al., Gold Bulletin 37, 72 (2004). [2]S. Lee et al., J. Am. Chem. Soc. 126, 5682 (2004); B. Yoon et al., Science 307, 403 (2005). [3]B.E. Salisbury et al., Chem. Phys. 262, 131 (2000); D. Stolcic et al., J. Am. Chem. Soc. 125, 2848 (2003)
148
POSTERS - SESSION B
B19
Ag islands on C60 functionalized Au(111) compared to deposited Ag clusters

Stefanie Due1 , Thomas Irawan1 , Torsten Richter1 , Benedikt Sieben1 , Chunrong Yin2 , Bernd von Issendor2 , Heinz Hvel1 1. Universitt Dortmund, Experimentelle Physik I, 44221 Dortmund, Germany 2. Universitt Freiburg, Fakultt fr Physik, 79104 Freiburg, Germany
We are interested in the electronic structure of clusters in contact with a surface. In addition to experiments with mass selected Ag clusters we grew Ag islands by evaporation of Ag atoms on a C60 functionalized Au(111) surface at a temperature below 50 K. The investigation of the silver islands with a low temperature scanning tunnelling microscope shows quite broad height distributions. Tempering the cluster/surface system up to dierent temperatures leads to a higher mobility of the silver islands and more and more coalescence. We observed a strong coalescence at temperatures above 150 K. These experiments can be compared with experiments of mass selected geometrically magic clusters deposited on C60 /Au(111) at room temperature and at T 165 K. Here we observed very narrow height distributions. We also studied the position of the clusters relative to the C60 molecules. We found out that the size selected clusters are on top of a C60 molecule and the grown islands at a position between two C60 molecules.
(a)
(b)
Figure 1: (a) Ag islands grown by silver atom deposition at T < 50 K and subsequent annealing to 265 K show a broad height distribution. Image size: 50 x 50nm2 . Height scale: 0 2 nm. (b) Ag309 clusters deposited at T 165 K. All clusters show the same height of h 2.65 nm. Image size: 65 x 65 nm2 . Height scale: 0 2.75 nm.
149
B20
POSTERS - SESSION B
Size-selected clusters on surfaces: Chemical and spectroscopic properties

Stefan Gilb Chair Physical Chemistry I, Technical University Munich, Germany
On the basis of specic examples taken from our laboratory, the most important steps in preparing size-selected metal clusters supported on thin oxide lms and investigating their chemical and spectroscopic properties are presented. The clusters are generated by a laser vaporization source. After mass selection in ultrahigh vacuum the clusters are softlanded on various substrates. Temperature programmed reaction spectroscopy, Fourier-transformation infrared spectroscopy as well as absorption spectroscopy are available for probing the properties of the clusters. With these techniques, it will be shown that the reactivity of nanoscale systems is mainly dominated by quantum-size eects that govern the electronic spectra of clusters, by the structural dynamical uxionality of clusters, as well as by impurity-doping eects. Specic systems of various sizes will be presented. First, the CO oxidation catalyzed by mass selected gold cluster on MgO will be discussed. Secondly, cavity ringdown spectroscopy, a highly sensitive photoabsorption technique, will be discussed in detail. First results on monodispersed samples of Aun=1,2,4,8,20 are presented and discussed in conjunction with TD-DFT calculations.
150
POSTERS - SESSION B
B21
MD Simulations of Porous Single and Multiple Layers of Ge

Ari Harjunmaa1 , Jura Tarus2 , Kai Nordlund1 and Juhani Keinonen1 1. Accelerator Laboratory, University of Helsinki, P. O. Box 43, Helsinki FIN-00014, Finland 2. CSC - Scientic Computing Ltd., P. O. Box 405, Espoo FIN-02101, Finland
Porous semiconductor surfaces have been an object of interest ever since the discovery of the strong visible photoluminescence of porous Si at room temperature [1]. Porous lms are usually made using anodic etching or a similar top-down method. However, some attention has also been given to bottom-up methods such as low-energy cluster beam deposition (LECBD)[2],[3]. Using cluster beams, it is easier to grow multiple superimposed layers having dierent porosities, which can be used for waveguide applications. By switching between sputtering targets, it is also possible to create multielemental multilayers, which allows greater variety in the properties of the layers. The purpose of this study is to expand the results of our previous work, where we used classical molecular dynamics (MD) to simulate the deposition of Ge clusters on a Si surface in an eort to produce porous Ge lms [4]. More clusters are deposited at high energy (1 eV per atom) on the porous samples obtained in that study, with the goal of seeing how a porous surface would be able to sustain the high-energy cluster bombardment necessary for growing porous multilayers. We present the results for the high-energy depositions of forty 1018-atom Ge clusters on porous layers grown using clusters with energies of 10 and 100 meV per atom.
(a)
(b)
Figure 1: Atomic cross-sections of the high-energy layers deposited using an energy of 1 eV onto porous surfaces grown with a deposition energy of 10 meV (a) and 100 meV (b) per atom.
[1]L.T. Canham, Appl. Phys. Lett. 59, 1046 (1990). [2]P. Mlinon, P. Kghlian, B. Prvel, A. Perez, G. Guiraud, J. LeBrusq, J. Lerm, M. Pellarin and M. Broyer, J. Chem. Phys. 107, 10278 (1997). [3]D. Amans, S. Callard, A. Gagnaire, J. Joseph, G. Ledoux and F. Huisken, J. Appl Phys. 93, 4173 (2003). [4]A. Harjunmaa, J. Tarus, K. Nordlund and J. Keinonen, Eur. Phys. J. D, accepted for publication.
151
B22
POSTERS - SESSION B
Electrocatalysis on Size-Selected Cluster

Mayrhofer, K.J.J.; Wiberg, G.; Heiz, U.; Arenz, M. TU Mnchen, Lehrstuhl fr Physikalische Chemie; D-85748 Garching, Germany
The aim of our newly started research project is to understand the size-dependent electrocatalytic properties of metal particles supported on planar substrates. In contrast to previous studies, the investigated metal particles will be prepared in UHV utilizing a laser evaporation source, size selected in a quadrupole mass spectrometer, and softlanded onto dierent substrates. This procedure will allow for the rst time in electrochemistry the investigation of particle size eects in the non-scalable size regime, i.e., where the electronic, and thus electrocatalytic, properties of the particles change in a non-monotonic manner and are not scalable from the bulk properties. On these size-selected particles, electrocatalytic measurements will be performed focusing on processes occurring in polymer electrolyte membrane fuel cells (PEMFC). That is, the oxidation of hydrogen, the inuence of CO in the hydrogen fuel, methanol oxidation as well as the oxygen reduction reaction. By comparing clusters of less than 1nm in diameter, with nanoparticles of up to 5 nm in diameter (prepared by wet chemical means), important insights about the active reaction centers on nanoparticles and clusters are expected.
Figure 1: Comparison of the results from cyclovoltametry, CO bulk oxidation and Oxygen reduction reaction, showcasing the adsorption of OH and its impact on electrochemistry on the Pt electrode surface depending on the particle size.
152
POSTERS - SESSION B
B23
Liquid Drop Model for Supported Clusters

Veronika Semenikhina, Andrey Lyalin, Andrey Solovyov, and Walter Greiner Frankfurt Institute for Advanced Studies, Max von Laue Str. 1, 60438 Frankfurt am Main, Germany
We have performed a theoretical exploration of structure formation and stability of atomic clusters deposited on a surface. In order to describe energetics, stability and shape of an atomic cluster that interacts with a surface we adapt the simple Liquid Drop Model (LDM). In particular, we investigate the role of cluster - surface interaction in the stability and deformation of Ar clusters with number of particles N (ranging from 4 to 150 particles) deposited on a graphite surface (001). The proposed model takes into account the cluster-surface interaction as well as the cluster deformation due to the interaction with the surface. We proceed from the fact that the total energy of free clusters of noble gases can be predicted within LDM with high accuracy [1],[2]. In the present work we elucidate the applicability of LDM to the description of properties of deposited clusters of noble gases. We obtain a good agreement between the results of LDM and the results of numerical simulations based on the dynamical search of the most stable isomers forming in the cluster growth process. The numerical simulations were performed with the use of cluster fusion algorithm (CFA) [1],[2]. We demonstrate that LDM can be used for simple estimation of the shape, stability and energetics of deposited atomic clusters.
(a)
(b)
(c)
Figure 1: (a): binding energy per atom for Ar clusters deposited on a graphite surface (001) calculated within LDM (line) and CFA (dots); (b): free Ar55 cluster; (c): Ar55 deposited on a graphite (001) surface. This work is partially supported by the European Commission within the Network of Excellence project EXCELL, and by INTAS under the Grant No. 03-51-6170.
[1]I.A.Solovyov, A.V.Solovyov, W.Greiner et al., Phys. Rev. Lett. 90, 053401 (2003). [2]I.A.Solovyov, A.V.Solovyov, W.Greiner, Int. J. Mod. Phys. 13, 697 (2004). [3]V.V. Semenikhina, A. Lyalin, A. Solovyov, and W. Greiner in preparation for JETP (2007).
153
B24
POSTERS - SESSION B
Inner-shell photoelectron spectroscopy of size-selected Cu-clusters on Si

N. Ferretti, B. Balkaya, M. Neeb, and W. Eberhardt BESSY, Albert-Einstein Str. 15, D-12489 Berlin-Adlershof
XPS and XANES spectra of supported Cun -clusters up to n=70 atoms have been measured with soft X-ray synchrotron radiation and are compared with the respective bulk spectra. The clusters were produced by a magnetron sputter cluster source and mass-selected prior to deposition by a magnetic sector eld. After passing the magnetic mass lter an individual cluster mass was softly landed onto a biased Si-wafer substrate. A cluster coverage of 5x1012 cluster (100 pA) was reached within 30 minutes for each sample.
XANES spectra (Cu-L3 -edge) of individual cluster sizes are exemplarily shown in the adjoining gure. With respect to the bulk, the L3 -edge for all clusters is shifted to a higher absorption energy by 1-2 eV for small clusters [1] and converging smoothly towards the bulk value with increasing cluster size. Similarly, a blue shift of the core electron binding energy is observed which amounts to 1 eV for small clusters and converge towards the bulk value with increasing cluster size. The absorption energy is located within the ionization continuum, i.e. above the 2p-XPS threshold, indicating a closed d-shell of the supported Cu-clusters. Upon oxidation, as experimentally shown for an oxidized Cu1 0-sample, an excitonic peak below the 2p-XPS threshold reveals a charge transfer from the lled d-band towards oxygen. Another distinct dierence between the XANES spectra of the bulk and cluster is the missing ne structure [2]-[3] beyond the L3 edge at energies >936 eV for sizes smaller than 10 atoms. At a cluster size 13 atoms a second absorption feature arises at 938 eV (see gure) indicating a morphology change from at to 3-dimensional compact structures. The band gap of the supported clusters has been estimated from a rigid band model. A strong interaction between the Si-wafer and the Cu cluster is indicated by a clear deviation from the liquid drop model.
[1]N. Ferretti, B. Balkaya, A. Vollmer, M. Neeb, W. Eberhardt, J. Electron Spect. Relat. Phenom., in press. [2]H. Ebert, J. Sthr, S. Parkin, M. Samant, A. Nilsson, Phys. Rev. B 53, 16067 (1996). [3]T. Tiedje, J.R. Dahn, Y. Gao, K.M. Colbow, E.D. Crozier, D.T. Jiang, W. Eberhardt, Solid State Comm. 85, 161 (1993).
154
POSTERS - SESSION B
B25
DFT-Investigations of the Coalescence Behaviour of Small Magic Si Clusters on Surfaces

W. Quester, M. Schach, and P. Nielaba Department of Physics, University of Konstanz, 78457 Konstanz, Germany
Experimental results indicate that small magic Si clusters do not form islands of bulk Si on weakly interacting surfaces (HOPG). Therefore these clusters might be building blocks for new cluster materials. Earlier simulations [1] for Si4 were extended to Si7 and Si10 . Potential energy curves of two approaching Si clusters were calculated for dierent reaction channels using Density Functional Theory implemented in the CPMD code available at [2]. For Si7 it was shown that the cluster-cluster interaction is either repulsive or there are fusion barriers that block spontaneous fusion of clusters at sucient low temperatures. So far the potential energies found for dierent reaction channels of Si10 were repulsive or had minima which were too weak to be interpreted as covalent bonds. In the calculations neglecting the cluster-surface interaction none of the above mentioned clusters tends to form bulk Si. In the next step a graphite surface is included in the simulations to get a better match with experiments. The inuence of surface defects is studied as well.
[1]M. Grass, D. Fischer, M. Mathes, G. Gantefr and P. Nielaba, Appl. Phys. Lett., 81, 3810 (2002). [2]www.cpmd.org.
155
B26
POSTERS - SESSION B
Wn Sm -Clusters: Search for new nano-materials

W. Westhuser1 , T. Mangler1 , T. Fischer1 , N. Bertram1 , S. Gemming2 , G. Seifert2 , and G. Gantefr1 1. Department of Physics, University of Konstanz, Germany 2. Department of Physical Chemistry and Electrochemistry, University of Dresden, Germany
The bulk semiconductors WS2 and MoS2 form layered structures similar to bulk graphite. Therefore, small clusters of these materials might also build up cage-structures analogous to the famous C60 . Small Wn Sm - and Mon Sm -clusters are studied theoretically using density functional theory and experimentally with photoelectron spectroscopy of gas phase clusters [1], [2]. These studies reveal magic species with a high stability, which might be suitable as a building block for new cluster materials. In contrast to graphite, the larger species form nanoplatelets with triangular shape [3]. To investigate the suitability as building blocks for new cluster materials, size-selected Wn Sm clusters are deposited in soft-landing mode on Ag(111) and SiO2 /Si surfaces at ultrahigh vacuum conditions. These samples are analyzed using electron energy loss spectroscopy (HREELS), and X-ray photoelectron spectroscopy (XPS). The data are compared to bulk WS2 .
[1]N. Bertram, Y.D. Kim, G. Gantefr, Q. Sun, P. Jena, J. Tamuliene and G. Seifert, Chem. Phys. Lett. 396 (2004), 341 [2]S. Gemming, J. Tamuliene, G. Seifert, N. Bertram, Y.D. Kim and G. Gantefr, Appl. Phys. 82 (2006), 161 [3]N. Bertram, J. Cordes, Y.D. Kim, G. Gantefr, S. Gemming and G. Seifert, Chem. Phys. Lett. 418 (2006), 36
156
POSTERS - SESSION B
B27
Nanocluster Metrology: Mass-spectrometry and shape determination using size-selected clusters

N.P. Young, Z.Y. Li, S.Palomba, Y. Chen, R.E. Palmer Nanoscale Physics Research Laboratory, School of Physics & Astronomy, University of Birmingham, Edgbaston, Birmingham B15 2TT, United Kingdom neily@nprl.ph.bham.ac.uk
Clusters are often referred to as nanoscale building blocks, with physical and chemical properties that vary signicantly with size. Mass-selected cluster beam deposition has allowed detailed studies of such size-dependent phenomena. However, mass-selected beams are not always accessible, or indeed appropriate in certain cluster-based applications. For example, the catalytic activity of nanoparticles is well known to be associated with cluster size and shape. However the exact atomic mass of catalytic nanoparticles is often a poorly dened quantity; a diculty exacerbated by the sintering of supported particles during processing. Additional methods of accurate nanoscale characterisation are required to further comment upon structural and size-dependent phenomena. Characterisation of supported clusters has traditionally advanced via spectroscopic analysis or microscopical imaging techniques. The former often only provides average values of a collection of clusters, while imaging methods are generally limited to measurements of spatial dimensions, often providing only a two-dimensional view of the three-dimensional cluster. In the present study, we report on the successful application of high-angle annular dark eld scanning transmission electron microscopy (HAADF-STEM) to quantify a range of supported Au nanoclusters in terms of their atomic mass. When only electrons scattered through large angles are collected, HAADF image contrast is strongly related to the type and number of atoms within a crystalline atomic column [1]. Deposited mass-selected clusters are a model system to study using HAADF-STEM, since their well dened size allows for the prospect of calibrating HAADF image intensity as a function of cluster mass [2]. For clusters whose depth perpendicular to the substrate is sucient to maintain approximately incoherent imaging, a reliable calibration curve of scattered electron intensity as a function of cluster mass was obtained. The resulting empirical knowledge allowed the atomic mass of other unknown Au nanoparticles to be deduced. Colloidal Au nanoparticles and Au islands deposited via vacuum sublimation are presented as two contrasting examples. Comparison of the estimated cluster mass with simple geometric models allows the overall three-dimensional cluster morphology to be deduced. Prediction of a quasi-spherical morphology for the colloids conrmed the capability of the method. The mass-spectrometry aspects of the technique are particularly suited to the sub 2-3 nm size range, and thus particularly appropriate to application in the characterisation of catalytic nanoparticles. The technique has advantages over traditional tomographic methods in terms of speed of acquisition of results. Metallic clusters from two to several thousand atoms in size may be characterised. Large clusters, in excess of 104 atoms are inaccessible due to the large projected column depth and crystal twinning eects at this size.
[1]A. Singhal, J.C. Yang, J.M. Gibson, Ultramicroscopy 67, 191 (1997). [2]Z.Y. Li, N.P.Young et al. Submitted
157
B28
POSTERS - SESSION B
Three-dimensional atomic-scale structure of size-selected gold nanoclusters

Z.Y. Li1 , N.P. Young1 , M. Di Vece1 , S. Palomba1 , R.E. Palmer1 , A. Bleloch2 , B.C. Curley3 , R. L. Johnston3 , J. Jiang4 and J. Yuan4 1. Nanoscale Physics Research Laboratory, School of Physics & Astronomy, University of Birmingham, Edgbaston, Birmingham B15 2TT, United Kingdom 2. UK SuperSTEM Laboratory, Daresbury Laboratory, Daresbury, WA4 4AD, United Kingdom 3. School of Chemistry, University of Birmingaham, Edgbaston, Birmingham B15 2TT, United Kingdom 4. Department of Materials Science & Engineering, Tsinghua University, Beijing 100084, China neily@nprl.ph.bham.ac.uk
The aberration-corrected scanning transmission electron microscope (STEM) is used to study sizeselected gold nanoclusters, preformed in the gas phase [1] and soft-landed onto an amorphous carbon substrate. Atomic resolution high-angle annular dark eld (HAADF) imaging, coupled with image simulations using relaxed atomic coordinates provided by a genetic algorithm search, allows the identication of not only the size and shape, but also the atomic structure and orientation of the ultra-small Au309 magic number clusters. We show that structures can be identied with either decahedral or cuboctahedral geometries. This phenomenon is consistent with energetic considerations, specically, the existence of many local minima with relatively small energy barriers between particularly structures [2]. The work illustrates a new and very promising way to study structure and stability of supported ultra-small metal clusters in the nanometre size range, e.g. catalyst particles, with single atom sensitivity.
[1]S. Prantontep, S. J. Carroll, C. Xirouchaki, M. Streun, R. E. Palmer, Rev. Sci. Instrum. 76, 045103 (2005) [2]B.C. Curley et al, Submitted to JPC
158
POSTERS - SESSION B
B29
Thin-lm Eects on MgO/Mo-supported Au clusters

Pentti Frondelius1 , Hannu Hkkinen1,2 , Karoliina Honkala2 1. NanoScience Center / Department of Physics, University of Jyvskyl, P.O. Box 35, Jyvskyl, FIN-40014, Finland 2. NanoScience Center / Department of Chemistry, University of Jyvskyl, P.O. Box 35, Jyvskyl, FIN-40014, Finland
The adsorption of small gold clusters on Mo(100) supported MgO(100) ultra thin lms was studied by the means of the density functional theory [1]. The optimal geometries, adsorption energies (g. 1) as well as the charge states of the clusters of up to six atoms were investigated systematically both on regular and defected surfaces. It was found that the Mo(100) support induces clear changes to all the cluster properties compared to the adsorbates on a single crystal MgO(100). On a regular MgO/Mo at cluster geometries wetting the surface are energetically the lowest ones while on a single crystal MgO the best geometries are upright or slightly tilted ones. Also the oxygen vacancy of a MgO/Mo stabilizes the at clusters compared to the vacancy on a single crystal MgO. On a MgO/Mo the adsorption energies of the clusters are increased compared to the adsorption energies on a single crystal MgO independent of the investigated site. However, on a terrace site the adsorption energy oscillates as a function of a cluster size which is not seen in the case of an oxygen vacancy. Furthermore the clusters gain more charge in the presence of the Mo metal. On a regular MgO/Mo the clusters become anionic while on a regular single crystal MgO they are essentially neutral. On an oxygen vacancy the clusters are charged both on a MgO/Mo and a single crystal MgO. The anionic nature of the adsorbates in the presence of a Mo lm explains the even odd oscillations in the cluster adsorption energy on a regular MgO/Mo. The dierence in the adsorption energies of the clusters between a single crystal MgO and a MgO/Mo substrates correlates with the electron anities of the clusters. The electron anity oscillates as a function of a cluster size leading to the oscillations in the adsorption energy.
Figure 1: The cluster adsorption energies on a regular MgO(100) (circles), on a regular MgO(100)/Mo(100) (lled circles), on an O vacancy of a MgO(100) (squares) and on an O vacancy of a MgO(100)/Mo(100) (lled squares).
[1]P. Frondelius, H. Hkkinen and K. Honkala, to be published.
159
B30
POSTERS - SESSION B
Softlanding, STM imaging and thermally activated cluster decay for Ag309 and Ag561 clusters on a C60 monolayer
Heinz Hvel1 , Stefanie Due1 , Thomas Irawan1 , Markus Bieletzki1 , Torsten Richter1 , Benedikt Sieben1 , Chungrong Yin2 , Bernd von Issendor2 , Michael Moseler3,4 1. Universitt Dortmund, Experimentelle Physik I, 44221 Dortmund, Germany 2. Universitt Freiburg, Fakultt fr Physik, Hermann-Herder Strae 3, 79104 Freiburg, Germany 3. Fraunhofer-Institut fr Werkstomechanik IWM, Whlerstrae 11, 79108 Freiburg, Germany 4. Freiburg Materials Research Center, Stefan-Meier-Strae 21, 79104 Freiburg, Germany
+ Mass selected Ag+ 5615 and Ag3093 clusters were deposited with low kinetic energy on an Au(111) surface functionalized with an ordered monolayer of C60 molecules. This substrate system proved to be a new and promising choice for the investigation of mass selected clusters attached to a surface. Stable cluster samples could be obtained for deposition at a temperature of 165 K, which in STM images measured at 77 K gave an extremely narrow height distribution with (3.10.2) nm and (2.60.2) nm cluster height, respectively. Molecular dynamics simulations of the deposition suggest that the experimental conditions indeed are close to softlanding with only minor distortions of the icosahedral cluster shape at the cluster-fullerene interface. After annealing the samples up to room temperature we observed thermally activated cluster decay and penetration of the Ag material though the C60 lm. Very interesting is the appearance of a sharp maximum at about 1.7 nm cluster height during the decay of the deposited clusters, which was also observed for room temperature deposition for a broad range of cluster sizes (55, 147, 309, 561, 923 atoms). This seems to be an indication for some magic cluster size in the cluster-surface system.
Figure 1: STM images measured at 77 K and height distributions for Ag309 clusters deposited on an Au(111) surface functionalized with 1 monolayer of C60 molecules. The left image shows the sample as deposited, the middle and right image after annealing to room temperature for 45 and 180 min, respectively. We observe cluster decay and the emergence of a magic metastable cluster height of 1.7 nm. The Ag material penetrates the C60 lm and forms monolayer islands below (cf. the line prole in the right image).
160
Dynamics
POSTERS - SESSION B
B31
Statistical Decay of C60

B. Climen, B. Concina, M.A. Lebeault, F. Lpine, B. Baguenard, C. Bordas Universit Lyon 1 ; CNRS ; LASIM UMR 5579, 43 boulevard du 11 novembre 1918, F-69622 Villeurbanne Cedex, France
Two experimental techniques have been combined to get a deeper insight into the decay of C60 excited by a nanosecond laser (355 nm). Our experimental set-up consists in a time-resolved velocity-map imaging spectrometer coupled with a time-of-ight mass spectrometer [1]. Time-resolved electron kinetic energy spectra were measured for the rst time on a large delay range (from 0.1 to 10 s). In addition to time-of-ight mass spectra, the ion formation was characterized by mass-resolved kinetic energy distributions, which is an original aspect of this contribution [2]. These three sets of experimental data are compared with a statistical model based on detailed balance: (1) ion time-of-ight spectra (2) time-resolved electron kinetic energy distribution giving direct access to delayed (thermionic) emission, and (3) mass-resolved ion kinetic energy distribution for C+ (44 2n 60). Ion time-of-ight mass spectra are compared to a Monte-Carlo simula2n tion. Parameters (activation energy and pre-exponential factor in the Arrhenius decay formula) characterizing C2 emission and delayed ionization agree with a similar study from the literature [3]. The temperatures extracted from the time-resolved kinetic energy distributions of the electrons give information on the activation energy and the pre-exponential factor for C2 emission from C60 [4]. The measured distributions in ion kinetic energy characterize the chains of sequential C2 emissions leading to the ion fragments. They are compared to a simulation of these decay chains using as inputs fragment temperatures from the Monte-Carlo simulation [2]. Agreement with the experiment is then achieved, conrming the validity of the statistical approach which describes three series of experimental data in the same frame.
[1]F. Pagliarulo, B. Climen, B. Baguenard, F. Lpine, M.A. Lebeault, A. Ollagnier, J. Wills, C. Bordas, Int. J. Mass Spectrometry 252, 100 (2006). [2]B. Climen, B. Concina, M.A. Lebeault, F. Lpine, B. Baguenard, C. Bordas, submitted to Chem. Phys. Lett. [3]B. Concina, S. Tomita, J. U. Andersen, P. Hvelplund, Eur. Phys. J. D 34, 191 (2005) [4]F. Lpine, C. Bordas, Phys. Rev. A 69, 53201 (2004)
163
B32
POSTERS - SESSION B
Delayed Electron Emission as a Probe of Finite-Size Properties of Small Carbon Clusters

F. Pagliarulo, B. Baguenard, B. Concina, F. Lpine, C. Bordas Universit Lyon 1 ; CNRS ; LASIM UMR 5579, 43 boulevard du 11 novembre 1918, F-69622 Villeurbanne Cedex, France
We have experimentally studied the electron emission from small carbon cluster anions excited by nanosecond laser (Xe:Cl, 308 nm, or Xe:Cl pumped dye laser). Time-resolved velocity-map imaging allows us to separate direct emission and delayed emission which is regarded as a statistical process. Kinetic energy spectra of emitted electrons from size-selected C (10 n 22) have been recorded n for a delay of 90 ns at = 308 nm showing only the contribution of delayed emission [1], [2]. In the framework of detailed-balance theory, the kinetic energy spectrum is shown to depend on the daughter temperature Td : P( )
exp
kB Td
with = 1 deriving from the assumption of a spherical daughter cluster interacting with the emitted 2 electron via a Langevin potential. Measured daughter temperatures Td are in good agreement with the detailed balance predictions. Wavelength dependent measurements at a given delay do not show any signicant variation of Td in accordance with the statistical approach. More interestingly, the shape of the kinetic energy distribution should be a promising way to study geometrical properties of small clusters or nite-size eects in general. Indeed, it is related to the cross-section of the reverse process within the detailed-balance formalism. A rst approach is to determine the exponent from the experimental spectra. A size-dependence is found: this parameter increases with the size from about 0.2 for n = 10 to about 0.5 for n > 17. A value of 0.5 corresponds to a (large) spherical cluster (with the assumption of a Langevin potential) but the interpretation for values signicantly dierent is not yet clear. Wavelength dependent measurements do not show any variation of . Thus, this parameter does not depend on the excitation process and seems to correspond to an intrinsic property of the cluster. PST calculations are underway to nd a relation between cluster properties (possibly geometry) and shape of the kinetic energy distribution.
[1]J.B. Wills, F. Pagliarulo, B. Baguenard, F. Lpine, C. Bordas, Chem. Phys. Lett. 390, 145 (2004). [2]F. Pagliarulo, B. Climen, B. Baguenard, F. Lpine, M.A. Lebeault, A. Ollagnier, J. Wills, C. ++ [3]Bordas, Int. J. Mass Spectrometry 252, 100 (2006).
164
POSTERS - SESSION B
B33
Sequential decay in clusters over long time scales: insights from phase space theory
F. Calvo1 , P. Parneix2 1. Laboratoire de Chimie et Physique Quantiques, IRSAMC, Universit Paul Sabatier, 118 Route de Narbonne, F31062 Toulouse, France 2. Laboratoire de Photophysique Molculaire, Bt. 210, Fdration Lumire-Matire, Universit Paris-Sud, F91405 Orsay, France
A general theoretical framework for describing the thermally induced sequential decay in atomic clusters is presented. Our scheme relies on a full treatment of individual dissociation steps based on phase space theory (PST), built into a kinetic Monte Carlo (kMC) procedure [1]. This combined PST/kMC approach allows us to follow the evolution of several statistical properties such as the size, the angular momentum, or the temperature of the cluster over arbitrarily long time scales. Quantitative accuracy is achieved by incorporating anharmonicities of the vibrational densities of states, the rigorous conservation of angular momentum via the eective dissociation potential, and a proper calibration of the rate constants. Our approach is tested and validated on selected Lennard-Jones (LJ) clusters in various situations, using molecular dynamics (MD) simulations as a benchmark. Several approximations, including a mean-eld rate equation treatment, are critically discussed. Finally, by coupling the present method with explicit non-adiabatic dynamical trajectories, the long time relaxation in electronically excited Ar+ can also be investigated [2]. n
Figure 1: Average cluster size for an initial LJ56 cluster thermally excited at several temperatures, obtained using our kMC method and compared with explicit MD simulations.
[1]F. Calvo and P. Parneix, J. Chem. Phys. 126, 034309 (2006). [2]work in progress.
165
B34
POSTERS - SESSION B
Directed Electron Emission from Metal Clusters Induced by Plasmon-Enhanced Excitation with Intense Femtosecond Laser Pulses
Thomas Fennel, Johannes Passig, Tilo Dppner, Christian Schaal, Josef Tiggesbumker, Karl-Heinz Meiwes-Broer Institute of Physics, University of Rostock, Universittsplatz 3, 18051 Rostock, Germany
Silver clusters AgN (N=500..2000) generated with a magnetron sputtering source are irradiated with intense dual femtosecond laser pulses (Ilaser =1013 ...1014 W/cm2 ). In previous experiments we have demonstrated that the charging of the clusters can be enhanced by the resonant excitation of the dipolar mode of the delocalized electrons. When tuning the optical delay of the dual pulses to achieve such plasmon enhanced ionization both the yield of highly charged ions and the maximum kinetic energy of the emitted electrons could be maximized [1],[2]. As an extension of these studies, here we present the results of energy and angular resolved measurements of the electron emission. The most energetic electrons are emitted along the laser polarization axis, induced by resonant plasmon excitation at optimum pulse delay (cf. Fig. 1). A microscopic analysis of corresponding semiclassical simulations indicates strong temporal beating in the electron emission at resonance and identies phase-matched electron-cluster recollisions leading to multi-plasmon deexcitation, to produce the observed directional preference of most energetic electrons [3].
Figure 1: Electron time of ight spectra of silver clusters irradiated with intense (8 x 1013 W/cm2 ) dual femtosecond laser pulses. At the optimum optical delay of t=1.3ps a clear dierence is observed for electrons emitted parallel (squares) and perpendicular (triangles) to the laser polarization axis. The straight lines are guides to the eye only.
[1]T. Dppner, Th. Fennel, Th. Diederich, J. Tiggesbumker, and K.-H. Meiwes-Broer, Phys. Rev. Lett. 94, 013401 (2005) [2]T. Dppner, Th. Fennel, P. Radclie, J. Tiggesbumker, and K.-H. Meiwes-Broer, Phys. Rev. A 73, 031202(R) (2006) [3]Th. Fennel, T. Dppner, J. Passig, Ch. Schaal, J. Tiggesbumker, and K.-H. Meiwes-Broer, submitted.
166
POSTERS - SESSION B
B35
Molecular wavepacket oscillations of ultracold Rb2 and optimal control of multi-photon ionization of Rb2 molecules in a MOT
A. Merli, F. Weise, S. Birkner, S. M. Weber, F. Sauer, L. Wste, A. Lindinger1 , W. Salzmann, T. G. Mullins, J. Eng, M. Albert, R. Wester, and M. Weidemller2 1. Institut fr Experimentalphysik, Freie Universitt Berlin, Arnimallee 14, D-14195, Berlin, Germany 2. Physikalisches Institut, Universitt Freiburg , Hermann Herder Str. 3, D-79104, Freiburg, Germany
Our long-term aim is the ecient formation and vibrational cooling of ultracold Rb2 molecules to their vibrational ground state by pump-dump like processes via an intermediate excited state, theoretical predicted by [1]. First pump-probe experiments with femtosecond light pulses in a dark SPOT magneto-optical trap were successfully performed in order to gain information about the molecular dynamic in the excited state of the Rb-Dimer. The observed wavepacket oscillation periods are depending from the cut-o of the spectral frequencies (made in the Fourier plane of a zero-dispersion compressor) in the pump pulse below the Rb atomic D1 and D2 resonances, respectively. Linear chirps of the excitation pulse inuence the pump-probe spectra. Measurements at dierent bright state fractions [2] of the trapped molecules provide advice about the origin of the molecules which are oscillating. By applying a closed feedback loop in order to optimize the ionization process of the rubidium dimers, two dominant frequency bands in the optimal spectrum were observed. The obtained data reveal the ionization process and the involved excited states.
Figure 1: Experimental Rb+ count rates as a function of pump-probe delay between the red excitation 2 pulse and the green ionization pulse. The oscillations reect the wavepacket dynamics in the excited state. The oscillation periods decrease as spectral cut-o in pump pulse is detuned from the Rb - D1 atomic resonance.
[1]C. P. Koch, R. Koslo, and F. Masnou-Seeuws, Phys. Rev. A 73, 043409 (2006). [2]C.G. Townsend, N.H. Edwards, K.P. Zetie, C.J.Cooper, J. Rink, and C.J Foot, Phys. Rev. A 53, 1702, (1996)
167
B36
POSTERS - SESSION B
Electronic Relaxation in Ag Nanoclusters

Marco Niemietz1 Markus Engelke1 , Young Dok Kim2 , and Gerd Gantefr1 1. Department of Physics, University of Konstanz, D-78457 Konstanz, Germany 2. Division of Nano Sciences and Department of Chemistry, Ewha Womans University, 120-750 Seoul, Korea
In small metal clusters, the density of electronic states is very much reduced compared to the bulk. Accordingly, many properties related to the electronic structure of matter can change dramatically for clusters. The low density of states in small clusters having large gaps between electronic states, inhibits Auger-like decay channels that are responsible for ultrafast relaxation of optically excited states in bulk metals. Phonon-assisted relaxation is also inhibited by the fact that the electronic level spacing is much larger than the typical energy of a phonon. Only multi-phonon processes can lead to the relaxation of an optically excited state, which is rather unlikely and referred to as the "phonon bottleneck". Thus, much longer relaxation times are expected for these clusters. In the presented work, the decay mechanism of excited electronic states in small Ag nanoclusters is studied using time-resolved photoelectron spectroscopy. In contrast to the expectation mentioned above, lifetimes below 1 ps were observed for most of the Ag (n < 22) studied here. The only n exception is the magic Ag with a relaxation time of 4 ps (Fig. 1). The observed fast relaxations 7 are discussed in view of their ability to undergo fast shape deformations [1]. This approach can also explain the slow relaxation of the rigid Aun - nanoclusters (> 1 ns, Fig.1) [2]-[4] and the extremely fast relaxation of the exible magic Al13 (200 fs) [3]-[5].
Figure 1: Examples of time-resolved photoelectron spectra of Ag [1] and Au [2],[3]. The photon 7 6 energies of the pump and probe pulses are 1.55 eV and 3.1 eV, respectively.
[1]M. Niemietz, M. Engelke, Y. D. Kim, and G. Gantefr, Phys. Rev. B, in press (2007). [2]M. Niemietz, P. Gerhardt, G. Gantefr and Y. D. Kim, Chem. Phys. Lett. 380, 99 (2003). [3]Y. D. Kim, M. Niemietz, P. Gerhardt, F. v. Gynz-Rekowski, and G. Gantefr, Phys. Rev. B 70, 035421 (2004). [4]P. Gerhardt, M. Niemietz, Y. D. Kim and G. Gantefr, Chem. Phys. Lett. 382, 454 (2003). [5]V. V. Kresin and Yu. N. Ovchinnikov, Phys. Rev. B 73, 115412 (2006).
168
POSTERS - SESSION B
B37
Time-resolved Pump/probe-Photoelectron Spectroscopy of Isolated Fullerene and Phthalocyanine Negative Ions

Oli T. Ehrler1 , Ji Ping Yang1 , Christian Rensing1 , Albert Sugiharto1 , Christof Httig2 , Andreas-N. Unterreiner3 , Horst Hippler3 , and Manfred M. Kappes1 1. Lehrstuhl fr Physikalische Chemie Mikroskopischer Systeme, Universitt Karlsruhe (TH), Kaiserstrasse 12, 76128 Karlsruhe, Germany 2. Lehrstuhl fr Theoretische Chemie, Ruhr-Universitt Bochum, Universittsstrasse 150, 44801 Bochum, Germany 3. Lehrstuhl fr Molekulare Physikalische Chemie, Universitt Karlsruhe (TH), Kaiserstrasse 12, 76128 Karlsruhe, Germany
Pump-probe spectroscopy in the gas phase opens up the possibility to study time constants and branching ratios of excited state dynamics in the ultimate intramolecular limit without any perturbing inuence of a matrix. We present experimental results on the spectroscopy of mass selected fullerene and phthalocyanine negative ions with 270 fs time resolution. We have measured pump/probe photoelectron spectra of mass-selected, near room temperature fullerenes C in the gas phase [1]. Excitation of a higher vibronic transition in the characteristic 60 near infrared absorption band was performed at a wavelength of 780 nm. Lifetime of the vibra tionally excited B (2 Eg ) state at a calculated energy of 1.26 eV was found to be = 2.2 0.2 ps. The main decay process corresponds to intramolecular radiationless transitions into ground state C . This is in contrast to neutral C60 for which pumping at the absorption onset (1.95 eV) leads 60 to predominantly intersystem crossing. Fourfold negatively charged metastable phthalocyanine tetrasulfonate ions with dierent center metal ions [MPc(SO3 )4 ]4 (with M = Cu, Ni, H2 ) were excited in the low energy wing of the intense Q-band band [2]. The temporal evolution of the transient photoelectron spectra shows multiexponential decay mechanisms with lifetimes ranging from approximately hundreds of femtoseconds to several tens of picoseconds. While in the closed-shell nickel compound, Q-band absorption populates the lowest excited singulet state which rapidly relaxes ( 250 fs) directly to the electronic ground state, CuPc shows a sequential decay due to non-adiabatic coupling involving three excited dublet congurations and lifetimes of 1 250 fs, 2 = 2.1 0.6 ps, and 3 = 83 11 ps. Contrarily, de-excitation in the sulfonated free base phthalocyanine occurs also through a competing tunneling electron loss channel in the excited state leading to a characteristic autodetachment feature in the photoelectron spectra. From extracted lifetimes the tunneling rate in the excited state can be estimated between ktunnel = 1.4 1010 s1 and 2.1 1012 s1 , more than ten orders of magnitude higher than measured in the ground state [3]!
[1]O.T. Ehrler, J.P. Yang, C. Httig, A.N. Unterreiner, H. Hippler, and M.M. Kappes, J. Chem. Phys., 125, 074312 (2006). [2]O.T. Ehrler, Thesis, Universitt Karlsruhe (TH), 2006. [3]K. Arnold, T.S. Balaban, M.N. Blom, O.T. Ehrler, S. Gilb, O. Hampe, J.E. van Lier, J.M. Weber, and M.M. Kappes, J. Phys. Chem. A, 107, 794 (2003).
169
B38
POSTERS - SESSION B
Temperature dependent femtosecond two-photon photoemission from ultra-thin MgO lms

Mihai E. Vaida, Tobias Gleitsmann and Thorsten M. Bernhardt Universitt Ulm, Institut fr Oberchenchemie und Katalyse
Ultra-thin insulating oxide lms were originally invented as support for nano-scale model catalysts. Investigations indicate that these thin lms have almost the same chemical and physical properties of their bulk analogs. In particular MgO(100) lm deposited onto Mo(100) single crystal exhibits the electronic properties of a wide band gap (6eV) insulator. On the other hand it allows applying the electronic spectroscopy, because charging eects are avoided due to the electron tunneling through the few monolayers lm. Epitaxially magnesia thin lms supported on a Mo(100) single crystal surface are produced in situ by evaporating magnesium in oxygen atmosphere. The lms composition and quality are analyzed by temperature programmed desorption spectrometry, Auger electron spectroscopy, and low energy electron diraction, respectively. Changes in the electronic structure of these lms induced by post deposition annealing were investigated via femtosecond two photon photoemission spectroscopy and electron energy loss spectroscopy.
170
POSTERS - SESSION B
B39
Dynamics in Atomic Clusters: Analysis and Control

Roland Mitri, Ute Werner, Melanie Nler, Vlasta Bonai-Kouteck Humboldt Universitt zu Berlin, Institut fr Chemie, Brook-Taylor-Strasse 2, 12489 Berlin, Germany
We present study of dynamics and ultrafast observables in the frame of pump-probe negative-toneutral-to-positive ion (NeNePo) and time-resolved photoelectron spectroscopy (TRPES) in context of cluster reactivity [1],[2]. This will be illustrated on examples of pure and mixed silver-gold trimers and their complexes with molecular and dissociated oxygen. First principle multistate adiabatic dynamics allows us to determine timescales of dierent ultrafast processes and conditions under which these processes can be experimentally observed. Furthermore, we present a strategy for optimal control of ultrafast processes by shaped infrared laser elds based on the quantumchemical MD on the y and our Wigner distribution approach [1], in context of isomerization in clusters, biomolecules and their complexes. The shapes of pulses can be assigned to underlying processes and therefore optimal control can be used as a tool for analysis.
[1]V. Bonai-Kouteck, R. Mitric, Chem. Rev. 105, 11 (2005). [2]V. Bonai-Kouteck, R. Mitric, U. Werner, L. Wste, R. S. Berry, Proc. Natl. Acad. Sci. 103, 10594 (2006).
171
B40
POSTERS - SESSION B
New reactivity-promoting criterion based on internal vibrational energy redistribution

Roland Mitri, Christian Brgel, and Vlasta Bonai-Kouteck Humboldt Universitt zu Berlin, Institut fr Chemie, Brook-Taylor-Strasse 2, 12489 Berlin, Germany
We propose to introduce intrinsic dynamical properties as new criterion for promoting reactivity of small size noble metal reactive centers relevant for heterogeneous catalysis. In order to illustrate the concept, collisions between Ag or Au clusters and molecular oxygen have been investigated 6 6 with direct ab-initio molecular dynamics using DFT. We show that dierent nature and eciency of internal vibrational energy redistribution (IVR) during reaction dynamics is responsible for signicantly dierent sticking probabilities of O2 to gold and to silver clusters. In the case of Au6 and O2 collisions, resonant IVR occurs between two subunits activating O2 and promoting subsequent reaction. In contrast, a dissipative IVR in Ag and O2 molecule prevents O2 to react with other 6 adsorbates. These ndings allow us to introduce the nature of IVR as new criterion for promoting reactivity of noble metal clusters: Resonant IVR between reactants promotes reactivity towards adsorbates.
172
POSTERS - SESSION B
B41
Analysis and Control of Metal Cluster and Adsorbat Complexes within the Framework of NeNePo-Spectroscopy
Shaohui Li, Juri Demuth, Bruno Schmidt, Waldemar Unrau, Xin Zhang, Aldo Mirabal, Torsten Siebert and Ludger Wste Institut fr Experimentalphysik, Freie Universitt Berlin, Arnimallee 14, 14195 Berlin, Germany
The presented work aims to further develop femtosecond time-resolved NeNePo (negative ion-toneutral-to-positive ion) spectroscopy towards studying the catalytic properties of noble metal clusters and the respective adsorbate complexes [1]. We seek to expand this spectroscopic technique to allow for a comprehensive characterization of the electronic structure and nuclear dynamics of the respective cluster system. This goal is pursued in order to ultimately achieve the capability of steering the cluster dynamics along a specic reaction coordinate and herby reach a desired reactive geometry via photo-excitation (see Fig. 1) [2]. Towards this goal, a tandem mass-spectrometer coupled with a hexadecapol ion trap allows for mass-selection of cluster anions, trapping and synthesis of adsorbate complexes, as well as a further mass-selection in the detection of the products generated by means of photo-excitation with ultrashort laser pulses. For the photo-excitation, femtosecond white-light pulses are generated by means of self-phase modulation through lamentation in noble gas atmosphere. This laser source provides pulses that span a spectral range form the visible to NIR and can be modulated by a liquid crystal modulator. Laser pulses with a specically tailored electric eld can be generated that drive the electron detachment and subsequent transitions in the cluster system so that the nuclear dynamics lead to the desired reactive geometry as shown in Fig. 1. [1], [2]
Figure 1: Potential energy scheme illustrating the controlled photo-excitation of a cluster system to a desired reactive geometry within the framework of femtosecond time-resolved NeNePo spectroscopy. The temporal distribution of the frequencies within the bandwidth of the laser pulse can be adapted optimally to the dynamics of the system for maximum eciency in reaching the desired nal state.
[1]"Analysis and Control of small isolated molecular systems," A. Lindinger, V. Bonacic-Kouteck, R. Mitric, D. Tannor, C. P. Koch, V. Engel, T. M. Bernhardt, J. Jortner, A. Mirabal, and L. Wste, In Analysis and Control of Ultrafast Photoinduced Reactions, O. Khn, L. Wste (eds.), Springer Series in Chemical Physics Vol. 87, Springer, Heidelberg, p25 (2007). [2]V. Bonacic-Kouteck, R. Mitric, U. Werner, L. Wste, and R. S. Berry, First Proc. Natl. Acad. Sci 103, 10594 (2006).
173
B42
POSTERS - SESSION B
Time-resolved photoelectron spectroscopy of gold-oxide clusters

Kiichirou Koyasu, Marco Niemietz, Matthias Gtz, and Gerd Gantefr Department of Physics, University of Konstanz, D-78464 Konstanz, Germany
Gold (Au) nanoparticles supported on metal oxides act as very active catalysts [1] although Au is quite inert in bulk form [2]. The catalytic activity has been shown for example for oxidation of CO at low temperature [3], and has stimulated many further investigations. Moreover, the importance of electron transfer from a metal oxide substrate to Au nanoparticles has been found [4], and hence pure and oxidized Au cluster anions [5],[6] have been studied. We have investigated the time evolution of the electronic structure in Aun O clusters in the gas m phase by femtosecond (fs) time-resolved photoelectron spectroscopy: The energy of the exciting photon is stored in the cluster and distributed over a limited number of degrees of freedom [7]. Using a photon energy of 3.1 eV for both, the pump and the probe pulse, Au2 O (Fig. 1) showed a long-lived excited state (peak A, > 10 ps) and two subsequently appearing peaks (B and C). The peaks B and C can be assigned to the fragments Au (Fig. 1b) and AuO (Fig. 1c). In this case, the cluster might remain in the excited state and directly dissociates into dierent fragment channels, which show dierent temporal behavior.
Figure 1: Time-resolved PES spectra of (a) Au2 O and PES spectra of (b) Au and (c) AuO . A long-lived (>10 ps) excited state (peak A) was observed, followowed by dissociation into Au (peak B) and AuO (peak C).
[1]A. Stephen K. Hashmi and Graham J. Hutchings, Angew. Chem. Int. Ed., 45, 7896 (2006). [2]B. Hammer and J. K. Nrskov, Nature, 376, 238 (1995). [3]M. Haruta, Catal. Today, 36, 153 (1997). [4]A. Sanchez, S. Abbet, U. Heiz, W.-D. Schneider, H. Hkkinen, R. N. Barnett, and U. Landman, J. Phys. Chem. A, 103, 9573 (1999). [5]L. D. Socaciu, J. Hagen, T. M. Bernhardt, L. Wste, U. Heiz, H. Hkkinen, and U. Landman, J. Am. Chem. Soc., 125, 10437 (2003). [6]M. L. Kimble, A. W. Castleman, Jr., R. Mitri, C. Brgel, and V. Bonai?-Kouteck, J. Am. Chem. Soc., 126, 2526 (2004). [7]G. Lttgens, N. Pontius, P. S. Bechthold, M. Neeb, and W. Eberhardt, Phys. Rev. Lett., 88, 076102 (2002).
174
POSTERS - SESSION B
B43
Dynamics of O2 Photodesorption from Metal Clusters: A Signicant Dierence from Bulk Behaviour
Matthias Gtz1 , Marco Niemietz1 , Kiichirou Koyasu1 , Young Dok Kim2 , and Gerd Gantefr1 1. Department of Physics, University of Konstanz, D-78457 Konstanz, Germany 2. Division of Nano Sciences and Department of Chemistry, Ewha Womans University, 120-750 Seoul, Korea
The surprising catalytic properties of small noble metal clusters and nanoparticles [1]-[5] motivate the research on the reaction dynamics and photochemistry of such particles [6]. The interaction of oxygen with metal surfaces has been suggested to be one of the most important elementary steps in heterogenous catalysis [7]. Photodesorption of O2 from size-selected Agn O cluster anions with 2 n = 2, 3, 4 and 8 corresponding to the process Agn O + Agn O Ag + O2 was studied in n 2 2 the gas phase using time-resolved photoelectron spectroscopy. The spectra indicate that relaxations of photo-excited Agn O clusters with n = even numbers accompany ultrafast direct O2 photodes2 orption. For the odd-numbered cluster Ag3 O , in contrast, a long-lived excited state is observed, 2 since O2 might be dissociatively chemisorbed, suppressing direct photodesorption of oxygen. Both, direct desorption and long-lived excited states, have not been observed from adsorbate covered metal surfaces, suggesting unique photochemical properties of such small clusters.
Figure 1: Series of photoelectron spectra recorded using a probe pulse of 1.55 eV after photoexcitation of Ag2 O with 3.1 eV [8]. The experimental data display each state of the process: The 2 excitation into a well dened electronic state (light background), its decay via desorption of O2 and the appearance of the bare metal cluster (dark background).
[1]A. Sanchez, S. Abbet, U. Heiz, W.-D. Schneider, H. Hkkinen, R. N. Barnett, and Uzi Landman, J. Phys. Chem. A 103, 9573 (1999). [2]W. T. Wallace and R. L. Whetten., J. Am. Chem. Soc. 124, 7499 (2002). [3]M. Haruta, Catal. Today, 36, 153 (1997). [4]M. Valden, X. Lai, and D. W. Goodman, Science 281, 1647 (1998). [5]D. C. Lim, I. Lopez-Salido and Y. D. Kim, Surf. Sci. 598, 96 (2005). [6]L. D. Socaciu-Siebert, J. Hagen, J. Le Roux, D. Popolan, M. Vaida, S. Vajda, T. M. Bernhardt and L. Wste, Phys. Chem. Chem. Phys. 7, 2706 (2005). [7]T. S. Kim, J. D. Stiehl, C. T. Reeves, R. J. Meyer, and C. B. Mullins, J. Am. Chem. Soc. 125, 2018 (2003). [8]M. Niemietz, M. Engelke, Y. D: Kim, and G. Gantefr, accepted in Appl. Phys. A (2007).
175
Reacted Clusters and Catalysis
POSTERS - SESSION B
B44
Transition Metal Cluster-CO Complexes

A. Fielicke1 ; P. Gruene1 ; G. von Helden1 ; G. Meijer1 ; I. Swart2 ; B. Weckhuysen2 ; F. de Groot2 ; D. B. Pedersen3 ; B. Simard3 ; D. M. Rayner3 1. Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin, Germany 2. Inorganic Chemistry and Catalysis, Utrecht University, Sorbonnelaan 16, 3584 CA Utrecht, The Netherlands 3. Steacie Institute for Molecular Sciences, NRC, 100 Sussex Drive, Ottawa, Ontario, Canada
The adsorption of carbon monoxide is a common probe to characterize the surfaces of transition metals or of deposited transition metal nanoparticles. Furthermore, the interaction of CO with transition metals directly plays a central rule in model studies of catalytic oxidations or, e.g., in the Fischer-Tropsch reaction. The characterization of the bonding situation of the CO can be achieved using vibrational spectroscopy of the (CO) stretch, since the C-O bond strength is highly sensitive to the coordination of the CO and the electron density on the metal. Here, Infrared Multiple Photon Dissociation (IR-MPD) spectroscopy is used to study the interaction of CO with transition metal (Co, Rh, Ni, Au) clusters containing 2 to more than 30 metal atoms. IR spectra are measured in the range of the (CO) vibration for complexes of neutral, cationic and anionic clusters. The detection of a (CO) band and its position directly gives information on the adsorption state of the CO molecule (dissociative or molecular, atop or bridging conguration). In the case of rhodium we nd that for most clusters molecular adsorption in an atop position (1 ) is preferred; however for some clusters CO in bridging (2 ) or hollow (3 ) sites can be identied as well.[1] For atop bound CO ligands on charged clusters, the (CO) frequency shifts with cluster size and a quantitative model is developed to explain this size dependence taking into account the eect of M C back bonding and electrostatic interactions.[2] The gas phase experiments provide reference data on particles with dened charge states to gauge the charging of deposited clusters and can thereby give new insights into mechanisms of catalytic reactions involving electron transfer. A second focus will be given to saturated cluster carbonyls. For these systems, the vibrational spectra have been extended into the range of the M-C stretches as well as M-CO bending modes that are located in the far-infrared. For gold clusters, the structure of the clusters saturated with CO can be compared to the structure of the bare clusters. In certain cases we nd evidence suggesting that successive adsorption of CO can distort the metal cluster framework.[3] Finally, we present vibrational spectra of the cations of "classical" cluster carbonyls like Co2 CO+ Co4 CO+ or Rh6 CO+ that can be compared to the 8 12 16 neutral counterparts. Our initial results suggest that the structure of the cations in the gas phase can be dierent to the neutral species.
[1]A. Fielicke, G. von Helden, G. Meijer, D. B. Pedersen, B. Simard, and D. M. Rayner, J. Phys. Chem. B, 108, 14591 (2004). [2]A. Fielicke, G. von Helden, G. Meijer, D. B. Pedersen, B. Simard, and D. M. Rayner, J. Chem. Phys., 124, 194305 (2006). [3]A. Fielicke, G. von Helden, G. Meijer, D. B. Pedersen, B. Simard, and D. M. Rayner, J. Am. Chem. Soc., 127, 8416 (2005).
179
B45
POSTERS - SESSION B
Size selective reactivity of Cobalt clusters for the reaction with benzene and ethane
Britta Pfeer, Stephanie Jaberg, Gereon Niedner-Schatteburg Fachbereich Chemie, Physikalische Chemie,TU Kaiserslautern,Erwin-Schrdinger-Str. 52, 67663 Kaiserslautern, Germany
We investigate the size dependent reactivity of Co . Cationic and anionic cobalt cluster are pron duced in a laser vaporisation source and the ion reactions are investigated by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS). Benzene reacts with metal clusters via two dierent reaction pathways [1],[2]. It either adsorbs intact to the cluster surface or disintegrates under complete dehydrogenation. The cationic cobalt cluster only adsorb intact benzene. Co show n the intact adsorption for large clusters (n=9-13). Smaller cluster react under complete dehydrogenation. As already known from former studies [3] the reaction of metal cluster with hydrocarbons may be strongly size dependent. Co does no react with ethane, cationic clusters do react under H2 n elimination and with size dependent eciencies: this reaction takes place only for Co+ (10 n n 16). The reactivity is high for odd and low for even cluster sizes. In further studies we want to investigate the inuence of attached argon molecules on the cluster on the reactivity. It would be interesting to see if the "argon cooling" leads to a higher reactivity for the cobalt cluster as has been seen for platinum [4].
[1]C. Berg, M. Beyer, U. Achatz, S. Joos, G. Niedner-Schatteburg and V. Bondybey, J. Chem. Phys. 108, 5398 (1998). [2]G. Niedner-Schatteburg et al., Nb-heteroaromates, in preparation. [3]I. Baltenau, O. Balaj, M. Beyer, and V. Bondybey, Int. J. Mass Spectrom. 255, 71 (2006). [4]U. Achatz, M. Beyer, S. Joos, B. Fox, G. Niedner-Schatteburg and V. Bondybey, J.Phys. Chem. A. 103, 8200 (1999).
180
POSTERS - SESSION B
B46
Reactions of V4 O+ with small alkanes 10

Jens Dbler, Joachim Sauer Theoretical Chemistry, Humboldt University Berlin, Unter den Linden 6, Berlin, 10099, Germany
We study the reaction of V4 O+ with methane and propane using density functional theory and 10 compare the results to mass spectroscopic experiments. All calculations are performed with TURBOMOLE 5.8, using the B3LYP functional and the TZVP basis set. V4 O+ is a radical cation with 10 a V-O group and thus highly reactive. For the reaction with methane we nd a barrierless reaction forming V4 O9 OH+ CH3 with a reaction energy of 122 kJ/mol. In the experiment under single collision conditions V4 O10 H+ is found as product [1], corresponding to methyl loss. The fact that a reaction occurs under single collision conditions is consistent with a barrierless reaction. The reaction of V4 O+ with propane is more complex. The ionization potential of propane is lower 10 than that of methane and it is also lower than the IP of V4 O+ . Thus the encounter complex of the 10 reaction is not the electronic ground state and even an elastic collision concurrent with an electron transfer corresponds to an energy gain. This result is in agreement with the occurrence of C3 H+ in 8 experiments. The study of the initial reaction step is not straightforward with theoretical methods due to the excited nature of the electronic state. From the methane results it can be assumed that a hydrogen transfer to the V-O will be the rst step, as propane is more reactive than methane. Two dierent possibilities exist, leading to a primary or secondary propyl radical. The formation of the secondary radical is energetically favored, while the primary H abstraction is more likely due to statistics. In both cases structural optimizations did not yield a stable structure for a single hydrogen transfer. For the secondary H abstraction a second hydrogen atom of the propane interacts with the VOH group, preforming a propene molecule. The second hydrogen transfer, forming a VOH2 group and propene is subject to a shallow barrier. The primary hydrogen abstraction yields a propanol molecule attached to the vanadium via a rebound mechanism of the propyl radical to the VOH group and the propanol formation also barrierless. These barrierless mechanisms are in agreement with the experimental MS results, as V4 O10 H+ 2 (propene loss) and V4 O+ (propanol loss) are found under single collision conditions [2]. However, 9 the V4 O+ signal is small, indicating that propanol is only a side product. To look into this con9 tradiction, an MD simulation with a structure corresponding to the primary H abstraction was performed. The simulation reveals that a hydrogen shift from the secondary to the primary position of the propyl radical can occur. This path is driven by the higher stability of the secondary radical and will yield propene as product. The result that initial H abstraction from primary and secondary position can lead to the same reaction channel explains the occurrence of propene as main product and creation of propanol as a minor reaction channel. Additional experiments under multiple collision conditions yield V4 O9 OH2 C3 H+ as main product, due to attachment of excess 8 propane to V4 O9 OH+ . The calculated IR spectrum of V4 O9 OH2 C3 H+ is in good agreement with 2 8 an experimental IRMPD spectrum [3].
[1]S. Feyel, J. Dbler, D. Schrder, J. Sauer and H. Schwarz, Angew. Chem. Int. Ed. 45, 4681 (2006). [2]S. Feyel, D. Schrder and H. Schwarz, J. Phys. Chem. A 110, 2647 (2006). [3]G. Santamrogio, E. Janssens, J. Dbler, in preparation.
181
B47
POSTERS - SESSION B
Interaction of acetonitrile with Cobalt and Vanadium clusters

S. Jaberg, B. Pfeer, G. Niedner-Schatteburg Fachbereich Chemie, Physikalische Chemie, TU Kaiserslautern, Erwin-Schrdinger-Str. 52, 67663 Kaiserslautern, Germany
We continue to investigate the reactivity of transition metal [1],[2] yield with acetonitrile. Under +/ +/ single collision conditions the gas phase reactivity of Con and Vn clusters with acetonitrile (CH3 CN) is studied in a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer. We observed two dierent main reaction products: complete dehydrogenation in competition with intact adsorption of acetonitrile. Propensities depend on the cluster size. Small Co+ clusters favour n intact adsorption whereas larger clusters prefer complete dehydrogenation, such as all anionic cobalt +/ +/ clusters do (n=7-21). Stepwise addition of CH3 CN to Con or Vn leads to various products: either stepwise elimination of H2 is observed or the acetonitrile adsorb intact on the cluster surface. To compare the reactivity of dierent cluster sizes, kinetic studies were performed at background pressures of 8 1010 mbar and 1 109 mbar. The results of these studies are discussed in terms of simple reaction models.
[1]G. Niedner-Schatteburg et al., J. Chem. Phys. 102(12), 4870 (1995). [2]G. Niedner-Schatteburg et al., Nb-Heteroaromates, in preparation.
182
POSTERS - SESSION B
B48
A hollow tetrahedral cage of hexadecagold dianion provides a robust backbone for a tuneable sub-nanometer oxidation and reduction agent via endohedral doping
Michael Walter and Hannu Hkkinen Department of Physics, Nanoscience Center (NSC), University of Jyvskyl, Finnland
We show, via density functional theory calculations, that dianionic Au2 cluster has a stable, hollow, 16 Td symmetric cage structure, stabilized by 18 delocalized valence electrons. The cage maintains its robust geometry, with a minor Jahn-Teller deformation, over several charge states (q = -1,0,+1), forming spin doublet, triplet and quadruplet states according to the Hunds rules. Endohedral doping of the Au16 cage by Al or Si yields a geometrically robust, tuneable oxidation and reduction agent. Si@Au16 is a magic species with 20 delocalized electrons. We calculate a signicant binding energy for the anionic Si@Au16 /O complex and show that the adsorbed O2 is activated to a 2 superoxo-species, a result which is at variance with the experimentally well-documented inertness of Au anion towards oxygen uptake [1]. 16
Figure 1: a) Structure, b) electron localisation function and c) the electronic density of states of Si@Au16 . The jellium-derived delocalized states are indicated and visulaized in c).
[1]Michael Walter and Hannu Hkkinen, Phys. Chem. Chem. Phys. 8, 5407-5411(2006).
183
B49
POSTERS - SESSION B
The eect of gold doping on the reactivity of free silver clusters: Comparison of Ag+ and Ag2 Au+ 3
Denisia M. Popolan, Mihai E. Vaida, Thorsten M. Bernhardt Institut fr Oberchenchemie und Katalyse, Universitt Ulm, Albert-Einstein-Allee 47, Ulm, 89069, Germany
The chemistry of noble metal clusters was intensively studied in recent years. This is due to their fascinating properties acting as promising low temperature catalytic materials. However, the surprising reactive behavior is still far from being completely understood. Free gas phase clusters investigated by mass spectrometric methods might help to shed light on the reaction mechanisms and size eects in reactivity. Besides the pure free gold and silver clusters also mixed silver-gold clusters have been investigated. Insight into the active role of gold as a catalyst and into the possibilities of doping eects using gold atoms will help in the comprehension of the reactive properties of bimetallic clusters. Our investigations aim to elucidate the inuence on the reactivity when silver atoms in Agn clusters are replaced atom by atom. In this contribution results on the reactivity of Ag+ with carbon monoxide at temperatures between 100 and 300 K are presented. The eect 3 of introducing one gold atom on the chemical reaction kinetics is studied by comparison with the cluster Ag2 Au+ . The investigations are performed in a low energy ion beam apparatus consisting of a sputter cluster ion source and of a temperature variable octopole ion trap inserted into a multiple quadrupole mass spectrometer arrangement.
184
POSTERS - SESSION B
B50
Oxidation Reactions on Size-Selected Cluster Based Catalysts

Stefan Vajda1,2 , Gregory E. Ballentine1 , Stephanie Mucherie1 , Christopher L. Marshall3 , Jerey W. Elam4 , Michael J. Pellin5 , Byeongdu Lee6 , Chieh-Tsung Lo6 , Snke Seifert6 , Randall. E. Winans6 , Armin Kleibert7 , Kristian Sell7 , Viola von Oyenhausen7 and Karl-Heinz Meiwes-Broer7 Chemistry Division, 2 Center for Nanoscale Materials, 3 Chemical Engineering Division, 4 Energy Systems Division, 5 Materials Science Division, 6 X-ray Science Division, Argonne National Laboratory, 9700 South Cass Avenue, IL 60439, USA 7 Institut fr Physik, Universittsplatz 3, D-18051 Rostock, Germany
1
Introduction The objective of this work is to achieve high catalytic activity and selectivity in oxidative reactions by using highly monodisperse sub-nm size atomic metal clusters, as well as few nm size particles. The applied combination of techniques allows for ultimate control of both: surface composition, as well as catalytic particle size and composition - prerequisites in producing highly uniform active sites on technologically relevant supports [1]-[4]. Materials and Methods Support preparation. Our earlier studies on various oxide lms showed, that small Pt and Au clusters are exceptionally stable on thin alumina lms fabricated by atomic layer deposition (ALD) [5]-[6]. These lms were selected to pre-coat the anodized aluminum oxide (AAO) membranes and at silicon wafers prior to cluster and nanoparticle deposition. Using ALD, the diameter of the membrane pores was reduced to 10 nm. Catalyst deposition. Size-selected metal clusters and nanoparticles were produced for deposition in a continuous laser vaporization [6] and an arc cluster ion source (ACIS) [7]. Pt810 /Al2 O3 /AAO and Pt810 /SnO/Al2 O3 /AAO Catalyst Tests. The tests were performed under atmospheric pressure in a freestanding AAO ow reactor. Ag and Au Catalyst Tests. The performance of the catalysts was tested in a unique setup at the Advanced Photon Source which, at atmospheric pressure, allows for simultaneous mass-analysis and in situ acquisition of grazing incidence small angle X-ray scattering (GISAXS) images for a direct correlation of catalytic performance to particle size and shape. Results and Discussion ODH of Propane on Pt810 /Al2 O3 /AAO and Pt810 /SnO/Al2 O3 /AAO Catalysts. Selectivity towards propylene up to 85% were observed, depending temperature, presence of SnO promoter and location of the clusters in the membranes. Two to three orders of magnitude higher turn-over frequencies than those reported in the literature for the best Pt and VOx based catalysts were observed. The superb selectivity (only one or maximal two side-products) can be explained by very short contact times on highly uniform dispersed catalytic particles. Catalytic performance did not change even after lengthy heat treatment, thus indicating highly stable nanocatalysts. Oxidation of Ethylene and Propylene on Au and Ag Nanocatalysts. Onset of product formation was observed between 160-200 C. At higher reaction temperatures, silver particles tended to sinter, while gold clusters stabilized with a protective alumina overcoat retained their size.
[1]Bell, A. T., Science 299, 1688 (2003). [2]Heiz, U., Abbet, S., Hkkinen, H., and Landman, U., Materials Research Society Symposium Proceedings, 648, P9.1.1-P9.1.10. (2001) [3]Lee, S., Fan, C., Wu, T., and Anderson, S. L., J. Am. Chem. Soc. 126, 5683 (2004) [4]Valden, M., Lai, X., and Goodman, D.W., Science 281, 1647 (1998) [5]Vajda, S., Winans, R.E., Elam, J., Pellin, M.J., Seifert, S., Tikhonov, G.Y., and Tomczyk, N.A. Top. Catal. 39, 161 (2006) [6]Winans, R.E., Vajda, S., Elam, J., Lee, B., Pellin, M.J., Seifert, S., Tikhonov, G.Y., and Tomczyk, N.A. Top. Catal. 39, 145 (2006) [7]Methling, R.-P., Senz, V., Klinkenberg, E.-D., Diederich, Th., Tiggesbumker, J., Holzhter, Bansmann, G J., and Meiwes-Broer, K.H., Europ.Phys. J D 16, 173 (2001)
185
B51
POSTERS - SESSION B
Interaction of acetonitrile with Cobalt and Vanadium clusters

S. Jaberg, B. Pfeer, G. Niedner-Schatteburg Fachbereich Chemie, Physikalische Chemie, TU Kaiserslautern, Erwin-Schrdinger-Str. 52, 67663 Kaiserslautern, Germany
We continue to investigate the reactivity of transition metal [1],[2] yield with acetonitrile. Under +/ +/ single collision conditions the gas phase reactivity of Con and Vn clusters with acetonitrile (CH3 CN) is studied in a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer. We observed two dierent main reaction products: complete dehydrogenation in competition with intact adsorption of acetonitrile. Propensities depend on the cluster size. Small Co+ clusters favour n intact adsorption whereas larger clusters prefer complete dehydrogenation, such as all anionic cobalt +/ +/ clusters do (n=7-21). Stepwise addition of CH3 CN to Con or Vn leads to various products: either stepwise elimination of H2 is observed or the acetonitrile adsorb intact on the cluster surface. To compare the reactivity of dierent cluster sizes, kinetic studies were performed at background pressures of 8 1010 mbar and 1 109 mbar. The results of these studies are discussed in terms of simple reaction models.
[1]G. Niedner-Schatteburg et al., J. Chem. Phys. 102(12), 4870 (1995). [2]G. Niedner-Schatteburg et al., Nb-Heteroaromates, in preparation.
186
POSTERS - SESSION B
B52
Gas-phase Kinetic Studies on Reaction of Methane with [V3 O7 ]+

Xin Zhang, Shaohui Li, Ewald Janssens, Torsten Siebert, Knut R. Asmis, Ludger Woeste Xin Zhang, Shaohui Li, Ewald Janssens, Torsten Siebert, Knut R. Asmis, Ludger Woeste
Activation and functionalization of light hydrocarbon (C1 -C4 ) has attracted much attention because of its great importance in fundamental research and industrial application. Vanadium-oxide based catalysts have been widely used in oxidative conversion of light hydrocarbon, but detail reaction mechanism of light hydrocarbon on these catalysts is still unknown. Studies on the reaction of light hydrocarbon with gas-phase vanadium-oxide cluster ions by mass spectroscopy provide an eective rout to reveal the reaction mechanism [1]. Up to date, little attention has been paid to the reaction of methane with [V3 O7 ]+ , which is the smallest polynuclear vanadium-oxide cluster cation in the V5+ oxidation state and is considered to be more reactive than large vanadium-oxide cluster ions [2][3]. In this present work, reaction kinetics of methane with gas-phase [V3 O7 ]+ was investigated by radio-frequency ion-trap tandem mass spectrometer coupled with laser vaporization source. Possible reaction pathways and kinetic model on the reaction are proposed and the rate-limiting reaction steps as well as the eects of reaction conditions on rate constants are discussed here. During the reaction of methane with [V3 O7 ]+ at an ion-trap temperature of 100 120 K and CH4 partial pressure of 0.015 0.075 Pa, the activation of methane and the subsequent formation of [V3 O7 (CH4 )]+ , [V3 O7 (C2 H6 )]+ , [V3 O7 (C2 H4 )]+ , [V3 O7 (C2 H2 )]+ were observed. [V3 O7 (CH4 )]+ , [V3 O7 (C2 H6 )]+ and [V3 O7 (C2 H4 )]+ are intermediates and contentiously converted to the dominative product [V3 O7 (C2 H2 )]+ . The reaction of [V3 O7 ]+ with methane proceeds to equilibrium with the increase of the reaction time ( 6000 ms). The reaction goes through a pathway of ion-molecular association (1-1), coupling dehydrogenation (1-2) and contentious reversible dehydrogenation (1-3 and 1-4) described as,
[V3 O7 ]+ +CH4 [V3 O7 (CH4 )]+ [V3 O7 (CH4 )]+ +CH4 [V3 O7 (C2 H6 )]+ +H2 [V3 O7 (C2 H6 )]+ +CH4 [V3 O7 (C2 H4 )]+ +H2 [V3 O7 (C2 H4 )]+ +CH4 [V3 O7 (C2 H2 )]+ +H2
k1 (1) k2 (1) (1) k2 , k3 (1) (1) k4 , k4
(1)
(1-1) (1-2) (1-3) (1-4)
The ion-molecule association and coupling dehydrogenation reactions are involved in methane acti(abs) (1) of each reaction vation. The pseudo-rst-order rate constant kn and absolute rate constant kn step are respectively estimated according to the obtained kinetic data. The ion-molecule association is the rate-limiting step in the reaction. The reaction steps involving in methane activation are slow and the subsequent dehydrogenation steps are much faster. CH4 partial pressure and ion-trap (1) (abs) (1) (abs) temperature aected kn and kn of each reaction step. Moreover, kn and kn have a negative temperature and pressure dependency, due to the low-pressure limit of Lindemann mechanism and (1) (abs) the nature of ion-molecule reactions. The negative temperature dependence of kn and kn implies that there is no noticeable activation energy barrier for each reaction step under the reaction conditions.
[1]D.K. Bhme, H. Schwarz, Angew. Chem. Int. Ed. Engl. 44, 2236 (2005). [2]K.A. Zamsik, D.R. Justes, A.W. Castleman Jr., J. Phys. Chem. A 105, 10237 (2001). [3]S. Feyel, D. Schrder, X. Rozanska, J Sauer, H. Schwarz, Angew. Chem. Int. Ed. 45, 4677, (2006).
187
B53
POSTERS - SESSION B
Gas-phase chemistry of [SiAun ] , n = 1-4

Yali Cao, Martin Beyer Institut fr Chemie, Technische Universitt Berlin, Strae des 17. Juni 135, D-10623, Germany
It has been demonstrated that nanoscale gold particles can play an important role in catalysis, which has sparked interest in gold clusters in the gas phase [1],[2]. The Au-Si interfaces have been studied extensively owing to their importance in microelectronics. The group of Lai-Sheng Wang [3] has reported the electronic structure and photoelectron spectroscopy of anions [SiAun ]-(n=2-4), which revealed that the structures of [SiAun ] clusters were nearly identical to silicon hydride [SiHn ] molecules. We investigate the structure and reactivity of small gold-silicon cluster ions. Special focus lies on experiments which reect the gold-hydrogen analogy in [SiAun ] . In our experiments, [SiAun ] are produced by laser vaporization followed by supersonic expansion, stored in an FT-ICR mass spectrometer, and their reactions with a selection of small inorganic and organic molecules are investigated. Detailed insight and quantitative reaction rate constants are obtained by tting the time-intensity prole of reactant and product intensities to pseudo-rstorder kinetics. Quantum chemical calculations on selected species are employed to interpret the experimental ndings and to get quantitative information on the reaction potential energy surface.
[1]A. Sanchez, S. Abbet, A. U. Heiz, W.-D. Schneider, H. Hakkinen, R. N. Barnett, and U. Landman. J. Phys. Chem. A 103, 9573 (1999). [2]M. L. Kimble, A. W. Castleman, Jr., R. Mitri?, C. Brgel, V. Bona?i?-Kouteck. J. Am. Chem. Soc., 126, 2526 (2004). [3]B. Kiran, X. Li, H. J. Zhai, L. F. Cui, and L. S. Wang. Angew. Chem. Int. Ed. 43, 2125-2129 (2004).
188
POSTERS - SESSION B
B54
Catalytic Properties of Size-Selected Pt Clusters on TiO2 (110) Surface

Yoshihide Watanabe1,2 , Noritake Isomura1,2 , Hiroyuki Matsubara1 1. Toyota Motor Corporation 1200 Misyku Susono, Shizuoka, Japan 2. Toyota Central R & D Lab.Incs, Nagakute, Aichi 480-1192, Japan
Heterogeneous catalysts such as automotive exhaust catalysts consist of precious metal particle supported on oxide surfaces. The reduction of precious metal usage will be strongly required. Metal cluster has been speculated to have a strong size-dependence in catalytic activity. The cluster on the surface would give further specicity because of the interaction between the clusters and the surface. Our main purpose is the improvement of catalytic activity by cluster size control the interaction between the clusters and the surface. Catalytic oxidation of CO on size-selected Pt clusters on TiO2 (110) surface was investigated by high-pressure reaction cell (Fig.1). This high-pressure reaction cell was designed for high-pressure studies using small-area samples and a retractable internal isolation cell with quartz lining which constitutes a micro batch reactor in the 20kPa pressure range. The reaction cell and the external recirculation loop were connected to a stainless steel bellows pump for circulation.
(a)
(b)
(c)
Figure 1: (a) High-pressure reaction cell. (b) Overview of the experimental setup. (c) STM image of Pt10 /TiO2 (110). The size-selected Pt clusters were deposited on the TiO2 (110) surfaces prepared by the typical procedure using a new ultrahigh vacuum (UHV) cluster deposition apparatus supplied by the magnetronsputter ion source. Both crystal faces were cleaned by repeated Ar ion sputtering, and annealing, until a well-dened (1x1) LEED pattern was observed, and no impurities were detected by AES. The deposited Pt cluster and TiO2 surface was observed by a scanning tunneling microscope (STM). All of the chambers were connected with each other and the sample was transferred under UHV condition. This system is also equipped with LEED/AES and XPS/UPS (Fig. 2). The STM image (Fig. 3) show Ptn clusters deposited rmly on TiO2 surface without aggregation. The result of catalytic activity using high-pressure cell will be given.
189
Index
INDEX
List of Authors
Abd El Rahim, M., 56 Adilah, H., 127 Albert, M., 167 Alonso, J. A., 35, 88 Andersson, M., 138 Antoine, R., 56 Antonietti, J.-M., 22 Arenz, M., 100, 152 Armentrout, P., 44 Arndt, M., 38, 58 Asmis, K. R., 34, 187 Bttcher, A., 17, 128 Brgel, C., 172 Baguenard, B., 163, 164 Balkaya, B., 154 Ballentine, G. E., 185 Bansmann, J., 67 Bartels, C., 9 Belosludov, R. V., 7 Benoit, D., 106 Bernhardt, T. M., 105, 170, 184 Bertram, N., 156 Beyer, M. K., 33, 76, 188 Bieletzki, M., 160 Bierweiler, T., 91 Birkner, S., 167 Bleloch, A., 158 Blom, M. N., 61 Boese, A. D., 133 Boldyrev, A. I., 45 Bonai-Kouteck, V., 26, 171, 172 Bopp, J. C., 57 Bordas, C., 163, 164 Bostedt, C., 82 Bowen, K. H., 21 Bowers, M. T., 28 Brchignac, C., 116, 140 Broyer, M., 26, 46, 56 Bubek, M., 148 Bulut, F., 67 Burgert, R., 21 Cabria, I., 35 Cahuzac, P., 116 Calvo F., 165 Cao, Y., 188 Castleman Jr., A. W., 13 Chen, M., 43 Chen, Y., 157 Cheng, H.-P., 140 Cheshnovsky, O., 37 Chirot, F., 19, 96 Choi, C. H., 89 Christen, W., 115 Climen, B., 163 Compagnon, I., 26, 61 Compton, R. N., 18 Concina, B., 133, 163, 164 Conus, F., 147 Cordes, J., 21, 99 Curley, B. C., 158 Cwiklik, L., 55 Dbler, J., 81, 181 Dppner, T., 101, 166 Drner, R., 82 de Groot, F., 141, 142, 179 Del Vitto, A. , 22 Demuth, J., 102, 173 Deni, S., 25, 62, 119 Di Domenicantonio, G., 10 Di Vece, M., 158 Dietsche, R., 148 Due, S., 149, 160 Dugourd, P., 26, 56 Eberhardt, W., 49, 82, 154 Echt, O., 119 Egashira, K., 95 Ehrler, O. T., 131, 169 Elam, J. W., 185 Elliott, B. M., 57 Eng, J., 167 Engelke, M., 168 Flix, C., 10, 146, 147 Farajian, A. A., 7 Feiden, P., 116 Fennel, T., 166 Ferretti, N., 154 Fielicke, A., 75, 86, 141, 142, 179 Fischer, T., 82, 99, 156 Fournier, R., 83, 84 Frenzel, J., 137 Frondelius, P., 159 Furche, F., 90 Gde, S., 20, 87 Gtz, M., 99, 174, 175 Gantefr, G., 21, 82, 99, 148, 156, 168, 174, 175
193
INDEX Garand, E., 34 Gebhardt, R. K., 67 Gemming, S., 156 Getzla, M., 67 Gilb, S., 22, 150 Glaser, L., 70 Gleitsmann, T., 170 Gloess, A. N., 74 Goebbert, D. J., 34 Goodman, D. W., 43 Greiner, W., 27, 60, 68, 69, 79, 104, 111, 127, 130, 132, 153 Grubisic, A., 21 Gruene, P., 86, 179 Hkkinen, H., 77, 159, 183 Htting, C., 169 Hvel, H., 149, 160 Ha, D. G., 59 Hackermller, L., 58 Hammer, N., 57 Hampe, O., 85, 133 Harbich, W., 146 Harding, C.J., 100 Harjunmaa, A., 151 Hartl, K., 22 Headrick, J. M., 34, 57 Heiz, U., 22, 100, 152 Henriques, E., 104 Hervieux, P.-A., 120 Hillenkamp, M., 10 Hippler, H., 169 Hock, C., 9 Honkala, K., 159 Hrivnk, D., 121 Huber, B., 77, 103 Huwer, J., 9 Hwang, K. W., 59 Irawan, T., 149, 160 Isomura, N., 189 Jaberg, S., 48, 180, 182, 186 Jagoda-Cwiklik, B., 110 Jaksch, S., 145 Janssens, E., 102, 187 Jena, P., 21, 32 Jester, S.-S., 17, 128 Jiang, J., 158 Johnson, M. A., 34, 36, 57 Johnston, R. L., 158 Jones H. , 22 Joswig, J.-O., 137 Jungwirth, P., 55 Kalus, R., 121 Kappes, M. M., 17, 74, 85, 90, 91, 97, 128, 131, 133, 169 Karlick, F., 121 Kartouzian, A., 22 Kawazoe, Y., 7 Keinonen,J., 151 Ketterer, T., 148 Khanna, S. N., 13 Kiesewetter, G., 58 Kim, H. S., 89 Kim, N. D., 59 Kim, S. K., 59 Kim, Y. D., 148, 168, 175 Kiran, B., 21 Kleibert, A., 67, 185 Knickelbein, M. B., 76 Kondow, T., 95 Kordel, M., 97 Korol, A. V., 134 Koskinen, P., 77 Kostko, O., 90, 103 Koyasu, K., 174, 175 Krause, T., 115 Kubala, D., 119 Kulesza, A., 26 LHermite, J.-M., 19, 96 Ler, D., 17, 128 Lpine, F., 163, 164 Labastie, P., 19, 96 Lagutschenkov, A. , 109 Lang, S. M., 105 Lau, J. T., 78 Lebeault, M.A., 163 Lebedkin , S., 17 Lechtken, A., 90 Lecoultre, S., 147 Lee, B., 185 Lee, S. H., 59 Lee, Y.-T., 109 Lemaire, J., 133 Leygnier, J., 116 Li, S., 102, 173, 187 Li, X., 21 Li, Z. Y., 157, 158 Lim, K. H. , 22 Lim, C. T., 89 Lim, D. C., 148 Lindinger, A., 98, 167 Lineberger, W. C., 5 Liu, F., 44 Liu, S., 44 Lo, C.-T., 185
194
INDEX Lo, S., 134 Lopez, M. J., 35 Lyalin, A., 68, 69, 79, 104, 153 Mhr, I., 25, 62, 119 Mrk, T. D., 25, 62, 119 Mller, T., 78, 82 Matre, P., 133 Majima, T., 95 Mangler, T., 156 Marksteiner, M., 58 Marshall, C. L., 185 Martnez, J. I., 88 Martins, M., 70, 82 Masson, A., 140 Matheis, K., 131 Mathew, M., 130 Matsubara, H., 189 Mayrhofer, K. J. J., 152 McCunn, L., 57 Meijer, G., 24, 61, 75, 86, 141, 142, 179 Meiwes-Broer, K.-H., 20, 67, 82, 87, 101, 146, 166, 185 Merli, A., 167 Michalski, M., 22 Mirabal, A., 173 Mitri, R., 26, 171, 172 Mizuseki, H., 7 Moon, W. H., 89 Morgner, N., 90 Moseler, M., 8, 77, 103, 129, 160 Mucherie, S., 185 Mullins, T. G., 167 Nler, M., 171 Nakajima, A., 11 Nakamura, M., 120 Neeb, M., 82, 154 Neumaier, M., 85, 133 Neumark, D. M., 34 Neville, J., 82 Niedner-Schatteburg, G., 48, 109, 133, 180, 182, 186 Nielaba, P., 155 Niemietz, M., 168, 174, 175 Nishimiya, N., 139 Nordlund, K., 151 Novara, F., 63 Obolensky, O. I., 60, 104, 111, 132 Oelner, P., 82 Oger, E., 91 Oleksy, K., 121 Oomens, J., 61 Pacchioni, G. , 22 Pagliarulo, F., 164 Paizs, B., 61 Palmer, R. E., 157, 158 Palomba, S., 157, 158 Pankewitz, T., 109 Parneix, P., 165 Passig, J., 67, 101, 166 Pastewka, L., 129 Pedersen, D.B., 179 Pellin, M. J., 185 Peter, J., 22 Petersen, J., 26 Pfeer, B., 48, 180, 182, 186 Plewicki, M., 98 Polfer, N., 61 Popolan, D. M., 184 Przystawik, A., 20, 87 Quester, W., 155 Rsch, N. , 22 Rttgen, M., 100 Rhl, E., 82 Rabeus, S., 115 Rabin, I., 75 Radclie, P., 101 Rademann, K., 39, 115 Rasul, B., 145 Rayane, D., 56 Rayner, D. M., 47, 142, 179 Redlich, B., 141 Rensing, C., 169 Richter, T., 149, 160 Rittmann, J., 78 Rizzo, T. R., 23 Rodrigues, V., 147 Rosn, A., 138 Roscioli, J. R., 57 Rydlo, A., 147 Salzmann, W., 167 Santambrogio, Gabriele, 34 Sauer, F., 167 Sauer, J., 31, 81, 181 Scher, M., 82 Schaal, C., 166 Schach, M., 155 Schadow, T., 78 Scheier, P., 25, 62, 119, 145 Schmidt, B., 173 Schmidt, M., 140 Schmidt-Bcking, H., 82 Schnckel, H., 21
195
INDEX Schneider, H., 74 Schooss, D., 90, 97 Schrder, D., 63 Schwarz, H., 63 Scribano, Y., 106 Seifert, G., 137, 156 Seifert, S., 185 Sell, K., 185 Semenikhina, V., 153 Senz, V., 82, 101 Sieben, B., 149, 160 Sieber, C., 146 Siebert, T., 102, 173, 187 Sierka, M., 81 Simard, B., 179 Skruszewicz, S., 101 Solovyov, A. V., 27, 60, 68, 69, 79, 104, 111, 127, 130, 132, 134, 153 Solovyov, I. A., 27, 60, 79, 104, 127, 130, 132 Stairs, J. R., 90 Stanzel, J., 82 Stokes, S. T., 21 Sugiharto, A., 169 Suhai, S., 61 Sun, Y., 83, 84 Swart, I., 141, 142, 179 Tabarin, T., 26 Tan, L., 44 Tarus, J., 151 Terasaki, A., 95 Teslenko, V., 100 Thomas, H., 82 Tiago, M. L., 14 Tiggesbumker, J., 20, 82, 87, 101, 166 Uehara, T., 7 Ulbricht, H., 58 Unrau, W., 173 Unterreiner, A.-N., 169 v. Issendor, B., 9, 90, 103 Vaida, M. E., 170, 184 Vajda, S., 185 Vetter, K., 99, 148 Vitek, A., 73 Vogel, M., 78 von Helden, G., 61, 179 von Issendor, B., 37, 77, 78, 149, 160 von Oyenhausen, V., 185 Wste, L., 102, 167, 173 Wabnitz, H., 101 Walter, L., 97 Walter, M., 183 Walter, T., 48 Wang, L.-S., 6 Watanabe, Y., 189 Weber, J. M., 74 Weber, S. M., 98, 167 Weckhuysen, B., 141, 142, 179 Weidemller, M., 167 Weigend, F., 85 Weis, P., 17, 91, 128 Weise, F., 98, 167 Wellhfer, M., 70 Werner, U., 171 Wester, R., 167 Westhuser, W., 156 Whetten, R. L., 12 Wiberg, G., 152 Willis, M., 21 Winans, R. E., 185 Woeste, L., 187 Wurth, W., 70, 82 Xantheas, S. S., 109 Yakubovich, A. V., 27, 104 Yang, P. J., 169 Yin, C., 149, 160 Young, N. P., 157, 158 Yuan, J., 158 Zamith, S., 19, 96 Zamudio-Bayer, V., 78 Zappa, F., 25, 62, 119, 145 Zhang, M., 80 Zhang, X., 173, 187 Zhou, J., 34
196

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Contents

51 . 53 . 65 . 71 . 93 . 107 . 113 . 117 123 125 135 143 161 177

Index 191 List of Authors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193

Monday - Cluster Physics

MONDAY - CLUSTER PHYSICS

Time-resolved ionic caging dynamics

MONDAY - CLUSTER PHYSICS

Cage Clusters of Gold and Tin: Golden Buckyballs and Stannaspherene

MONDAY - CLUSTER PHYSICS

Transport Properties through Molecular Clusters by First-principles Calculations

MONDAY - CLUSTER PHYSICS

MONDAY - CLUSTER PHYSICS

Angle-resolved photoelectron spectroscopy of cold Na cluster anions

MONDAY - CLUSTER PHYSICS

Figure 1: Magneto-thermogalvanic voltage (MTGV) and GMR for Co clusters in Ag.

MONDAY - CLUSTER PHYSICS

MONDAY - CLUSTER PHYSICS

MONDAY - CLUSTER PHYSICS

From Designer Clusters to Synthetic Cluster Assemblies

MONDAY - CLUSTER PHYSICS

Evolution of magnetism in elemental clusters of transition metals

Tuesday - Clusters and Biomolecules

TUESDAY - CLUSTERS AND BIOMOLECULES

Size-Selected Carbon Cluster Materials

TUESDAY - CLUSTERS AND BIOMOLECULES

TUESDAY - CLUSTERS AND BIOMOLECULES

A novel nanocalorimeter device for free clusters

TUESDAY - CLUSTERS AND BIOMOLECULES

Photoelectron spectroscopy on mass-selected neutral silver clusters in helium nanodroplets

TUESDAY - CLUSTERS AND BIOMOLECULES

Unexpected Stability of Al4 H6 : A Borane Analog?

TUESDAY - CLUSTERS AND BIOMOLECULES

TUESDAY - CLUSTERS AND BIOMOLECULES

TUESDAY - CLUSTERS AND BIOMOLECULES

Infrared spectroscopic characterization of gas-phase clusters and cluster-adsorbate complexes

TUESDAY - CLUSTERS AND BIOMOLECULES

TUESDAY - CLUSTERS AND BIOMOLECULES

Photoabsorption and Photofragmentation in Nanoparticle-biomolecule Hybrid Systems

TUESDAY - CLUSTERS AND BIOMOLECULES

Phase Transition in Polypeptides: A Step towards the Understanding of Protein Folding

TUESDAY - CLUSTERS AND BIOMOLECULES

Wednesday - Clusters and Hydrogen

WEDNESDAY - CLUSTERS AND HYDROGEN

WEDNESDAY - CLUSTERS AND HYDROGEN

Materials for Hydrogen Storage: What can Clusters do?

WEDNESDAY - CLUSTERS AND HYDROGEN

Chemistry of Transient Species in Water Clusters

WEDNESDAY - CLUSTERS AND HYDROGEN

Probing Stepwise Hydration by Gas Phase Vibrational Spectroscopy

WEDNESDAY - CLUSTERS AND HYDROGEN

Interaction of hydrogen with graphitic nanostructures and hydrogen storage

WEDNESDAY - CLUSTERS AND HYDROGEN

WEDNESDAY - CLUSTERS AND HYDROGEN

WEDNESDAY - CLUSTERS AND HYDROGEN

WEDNESDAY - CLUSTERS AND HYDROGEN

Thursday - Cluster Chemistry

THURSDAY - CLUSTER CHEMISTRY

Catalytically active gold: from nano-particles to ultra-thin lms

THURSDAY - CLUSTER CHEMISTRY

Thermochemistry and Reactivity of Transition Metal and Metal Oxide Clusters

THURSDAY - CLUSTER CHEMISTRY

Many Faces of Aromaticity in Clusters

THURSDAY - CLUSTER CHEMISTRY