2284 J. Phys. Chem.

A 2010, 114, 22842292

Theoretical Infrared and Terahertz Spectra of an RDX/Aluminum Complex

Carlos Guadarrama-Perez, Julibeth M. Martnez de La Hoz, and Perla B. Balbuena*

Department of Chemical Engineering, Texas A&M UniVersity, College Station, Texas 77843
ReceiVed: October 18, 2009; ReVised Manuscript ReceiVed: December 13, 2009

Density functional theory is employed to characterize the infrared and terahertz spectra of an explosive
molecular species, RDX, deposited over an aluminum surface, modeled as a planar cluster of Al16. Changes
in the inter- and intramolecular vibrational modes are systematically analyzed starting from the isolated
monomer, dimer, and tetramer and then considering the interactions of the monomer with an Al plate. The
results are compared to available experimental information for RDX films on Al surfaces. It is found that the
RDX molecule changes conformation because of the interaction with the model Al surface, becoming closer
to an AAA conformation with the three NO2 groups in nearly axial positions. The calculated spectra serve as
an initial guideline to interpret the main peaks of previously reported RDX films on Al.

1. Introduction terahertz (THz) spectroscopy, holds some promise for effective

1,3,5-Hexahydro-1,3,5-trinitro-1,3,5-triazine, a nitramine com-
pound used in energetic materials, also known as hexogen,
cyclotrimethylenetrinitramine, cyclonite, or simply as RDX, is
a well-known explosive compound. The RDX molecule can be
found in several conformations; two of them are shown in Figure
1: one with two nitro groups in axial positions and one in the
equatorial position (AAE) and the other with the three nitro
groups in axial positions (AAA). Various RDX crystalline forms
exist: R, , , , and ,1 from which R is the most stable at bonded molecules can be detected. Lattice vibrations of
room temperature2 where crystal packing is stabilized by
CH O intermolecular interactions between a methylene and rotational (librational) motions can be seen almost exclu-
hydrogen of one molecule and oxygen atoms belonging to nitro
groups of a neighbor molecule.3 The form can be observed at
room temperature and pressure, when carefully crystallized after
cooling a very concentrated hot nitrobenzene solution.1 The
form has also been observed at ambient temperature but at high
pressures.4 The form has also been identified at high pressures,
with a crystalline structure characterized by the presence of two
molecules with different conformations, the first molecule with
two NO2 axial groups and the last NO2 group in an intermediate
position between equatorial and axial whereas the second
molecule has three nearly axial NO2 groups.5 Barriers for
interconversion among different RDX conformers range between
1.5 and 5 kcal/mol.6
Karpowicz and Brill7 measured Fourier transform infrared
spectra (FTIR) in vapor phase and in solutions, and in R- and
-forms. They discussed the existence of intermolecular forces
being responsible for the R form (Cs symmetry), stable in
crystalline state, while interactions with solvent molecules may
relax RDX molecules to a conformation where all three NO2
groups are located in equivalent positions (C3V symmetry).
Easy and fast identification of explosive materials, mainly in
airports and other public places, is crucial for implementing
efficient preventive security measurements. Present methods
used to identify the presence of explosive substances include
X-ray and -ray that pose some health risks to operators. On
the other hand, trace detection techniques are not infallible when
used with sealed containers. A relatively new technique,
* To whom correspondence should be addressed. E-mail: balbuena@
tamu.edu. Telephone: 979-845-3375. Fax: 979-845-6446.
explosives detection. It is based on the measurement of the
frequency-dependent response of a material to photons with
energies of about 1 meV. This technique is based on the same
principles used in FTIR, taking advantage of the light spectrum
in the range from 100 GHz to 4 THz (1 THz ) 100/3 cm-1). In
this region, located below the far infrared region and above
microwave radiation, beside others, intermolecular interactions
(weak bonds), skeletal bending modes through the entire
molecule, and intermolecular vibration modes of hydrogen-
molecules (also called external modes) consisting of translational
sively in this region.
Recent molecular dynamics simulations by Boyd et al.8 using
a new force field developed by the same authors9 reported the
RDX vibrational spectrum aiming to explain the origin of the
initial stages of detonation through the spread of lattice energy
to internal degrees of freedom, seeking doorway modes for this
energy. They compared the normal modes in two RDX
conformers with those of their crystal model, concluding that
motions involving nitro groups that correlate with significant
molecular center of mass motion may be involved in the energy
transfer from lattice to intramolecular vibrations as in shockwaves.
Melinger et al.10 deposited a RDX polycrystalline thin film
over an aluminum plate and, using waveguide terahertz time-
domain spectroscopy, measured near 10 K a spectrum consisting
of approximately 20 vibrational modes between 0.5 and 3.5 THz.
The spectrum of the film that was described as having planar
ordering on the inner surface of a metal parallel plate waveguide,
showing bands sharper than those reported in previous studies.10
It was reported that prior to the measurements the metal surface
was washed with solvent and then the plasma cleaned; however,
Figure 1. Most stable conformations of 1,3,5-hexahydro-1,3,5-trinitro-
1,3,5-triazine (RDX). The AAE form has one equatorial group while
AAA does not.

10.1021/jp909976d 2010 American Chemical Society

Published on Web 01/26/2010
Spectra of an RDX/Aluminum Complex
Figure 2. DFT calculated RDX structures at B3LYP/6-311G(d,p) level:
(a) AAE and (b) AAA conformers.
the authors did not provide details about the surface structure
or identify the corresponding modes.
DFT calculations are important tools to understand and
characterize spectroscopic information. Rice and Chabalowski11
have calculated, at a variety of theory levels (MP2/6-31G*,
B3LYP/6-31G*, and B3LYP/6-311+G**), three RDX con-
formers and their IR spectra from 700 to 1700 cm-1 and
compared them with experimental results, in order to explain
previous experimental results pointing to a gas-phase conforma-
tion where all NO2 groups are in axial positions and to a -form
solid RDX. Allis and co-workers12 simulated and analyzed the
solid-state terahertz spectrum of R-RDX using periodic DFT
calculations at a BP/DNP level of theory, reaching good
agreement with their measured polycrystalline RDX terahertz
spectra at 298 and 7 K.
An interesting extension of these studies is the analysis of
adsorbed RDX whether on surfaces or porous materials. In this
work we analyze changes in the molecular spectrum when the
RDX molecule is attached to a model aluminum surface using
first-principles DFT calculations, and we compare the results
to those observed by Melinger et al.10 We first compare IR
calculated spectra of AAE and AAA RDX molecular forms with
that calculated for a RDX molecule coordinated to an Al layer
and then with the published experimental spectrum for RDX
directly crystallized over an Al plate.10
2. Methods
The initial RDX molecular geometry taken from Cambridge
Crystallographic Data Base3 was optimized without restrictions
using the B3LYP/6-311G(d,p) model chemistry.13-16 In mono-
mers, dimer, and tetramer no negative frequencies were found,
Figure 3. Calculated IR spectra of AAE (black) and AAA (red) RDX conformers at B3LYP/6-311G(d,p) level of theory.
J. Phys. Chem. A, Vol. 114, No. 6, 2010 2285
indicating that the optimized geometries are local minima.
Tetramer and octamer geometries were taken from the published
experimental X-ray structural data3 and subsequently optimized.
To model RDX over Al, a single layer of Al16 was used to
simulate the Al surface. Al16 and Al16-RDX were optimized
using the same B3LYP/6-311G(d,p) method while restricting
Al displacements in the z direction perpendicular to the plane
of the surface. The calculated frequencies were not scaled, and
spectra taken from literature were digitized to compare experi-
mental and calculated data. In these comparisons, calculated
spectra were taken from the representation obtained with
Gaussview.17 All calculations were done with Gaussian03.18
Intermolecular interactions were interpreted using the NBO
population analysis.19,20
3. Results
Comparisons were made between calculated spectra for AAE
and AAA monomers, a tetramer, the Al16 layer, Al16-
AAA-RDX, experimental crystalline RDX, and RDX crystal-
lized over an Al plate, in order to assign vibrations to individual
peaks and interpret experimental spectra.
3.1. Comparison between AAE and AAA Conformers.
Our calculations in gas phase at the B3LYP/6-311G(d,p) level
indicate that AAE-RDX is 0.55 kcal/mol more stable than the
AAA conformer (Figure 2). Rice et al. had reported 0.19 kcal/
mol calculated at B3LYP/6-31G(d)6 and 0.64 kcal/mol at
B3LYP/6-311+G(d,p),11 in reasonable agreement with our
results.
Differences in bond distances and angles are not perceptible
between the AAE and AAA conformers, but the dihedrals
N2-C2-N3-N6 and N3-C2-N2-N5 are larger in AAA than
in AAE because of 1,3-diaxial repulsive interactions between
NO2 groups. A comparison of the AAE and AAA geometries
is included later in Table 3.
Comparison between the calculated AAE and AAA spectra
is shown in Figure 3. These spectra correlate very well with
the experimental ones reported previously.7 Near 3000 cm-1,
two bands corresponding to C-H stretching are observed for
AAA and three for AAE. This is because of symmetry
differences in both conformations. For AAE, two of these bands
(those closest to 3000 cm-1) correspond to a CH2 axial
stretching, and the most displaced corresponds to a CH2
2286 J. Phys. Chem. A, Vol. 114, No. 6, 2010 Guadarrama-Perez et al.

Figure 4. Calculated IR spectrum section (0-500 cm-1) for the AAE (black) and AAA (red) conformers.

TABLE 1: Bond Distances (), Angles (deg), and Dihedrals

(deg) for Dimer, Isolated AAE Molecule, and Octamer,
Calculated at B3LYP/6-311G(d,p)a
AAE octamer RDX crystal
parameter dimer monomer (average) (average)
N1-N4 1.39 1.40 1.39 1.36
N2-N5 1.43 1.43 1.41 1.41
N3-N6 1.43 1.43 1.42 1.41
N4-O1 1.22 1.22 1.22 1.23
N4-O2 1.22 1.22 1.22 1.23
N5-O3 1.21 1.21 1.22 1.22
N5-O4 1.21 1.21 1.22 1.22
N6-O5 1.21 1.21 1.22 1.22
N6-O6 1.21 1.21 1.22 1.22
Figure 5. RDX dimer minimal energy structure calculated at B3LYP/
C3-H3eq 1.08 1.08 1.08 0.93
6-311G(d,p) theory level.
C3-H3ax 1.10 1.10 1.09 0.96
C1-H1eq 1.08 1.08 1.08 0.93
equatorial stretching while in AAA one band is present due to C1-H1ax 1.10 1.10 1.09 0.96
C3-N1-N4 117.34 115.69 117.45 118.74
CH2 axial stretching and the other to CH2 equatorial stretching. C2-N3-N6 116.82 116.85 117.29 117.11
Three main groups of bands can be observed in the central C2-N2-N5 117.06 116.85 117.19 116.89
region of both spectra. One group around 1680 cm-1 is due to N3-C3-N1-N4 162.00 166.23 140.36 147.49
NO2 asymmetric stretching. The second group between 1200 N2-C2-N3-N6 96.08 95.94 109.83 91.12
and 1550 cm-1 is related to CH2 wagging, scissoring, and N3-C2-N2-N5 -97.17 -95.94 -96.34 -93.08
twisting vibrations, and the group between 750 and 1050 cm-1 a
Subscripts eq and ax indicate equatorial and axial distances
is due to CH2 rocking and NC2 stretching. respectively. The RDX crystal values are from published data.3
A significant difference between both spectra is the higher
intensity of a band in the IR spectrum of the AAE conformer
at 1300.5 cm-1 compared to that at 1296.4 in the AAA spectrum. S1) shows that there are six interactions of the kind
Both bands are due to CH2 wagging plus N-N bond stretching. nO1f*C3-H3eq (each one corresponding to a pair of electrons
Also, while just one band can be seen at 1677.8 cm-1 in the from the oxygen atom interacting with a CH antibonding orbital
AAA spectrum, accounting for asymmetric O-N-O stretching, of the neighbor molecule) responsible for formation of the dimer.
up to three bands are due to the same kind of vibration in the A detailed comparison of the geometric parameters between
AAE spectrum at 1645.9, 1670.2, and 1688.4 cm-1. Other the AAE monomer and dimer is displayed in Table 1, showing
differences can be observed near 500 cm-1, Figure 4, where some structural differences. Average parameters for the geom-
the most notorious is the shift of a band calculated at 326.3 etries of the calculated octamer and the experimental crystal
cm-1 in the AAE conformer (accounting for all CH2 rocking) are included for reference. In the dimer, N has less tetrahedral
which is equivalent to the one at 360.75 cm-1 in the AAA character (is more planar) probably because of the intermolecular
conformer spectrum. electronic interaction between NO2 and CH, revealed by the
3.2. Building Intermolecular Interactions: Monomer, smaller N1-N4 dimer distance and larger C3-N1-N4 angle
Dimer, Tetramer, and Octamer. The calculated minimal (Table 1) and by the NBO population analysis (Supporting
energy geometry of an RDX dimer in gas phase corresponds to Information, Table S1).
a system where both molecules are in AAE conformation, as A tetramer and an octamer were also calculated starting with
displayed in Figure 5. geometry obtained from a crystal containing eight molecules
Distances O1-H3eq and O1-H3eq are 2.33 , which is from the Cambridge Crystallographic Database and, in the case
below the van der Waals radii sum (2.72 ). Also a NBO of the tetramer, randomly selecting four of those molecules,
population analysis20 included as Supporting Information (Table initially all in AAE conformation. The tetramer optimized at
Spectra of an RDX/Aluminum Complex J. Phys. Chem. A, Vol. 114, No. 6, 2010 2287

Figure 6. Calculated spectra of AAE monomer (black), dimer (red), and tetramer (green) using B3LYP/6-311G(d,p) model chemistry.

Figure 7. (a) Amplification (0 to 150 cm-1) of AAE-RDX monomer spectrum (black), dimer (red), and tetramer (green) calculated with B3LYP/
6-311G(d,p) model chemistry. (b) Visualization of the calculated symmetric optical rotation at 17.3 cm-1 in RDX dimer.

B3LYP/6-311G(d,p) level resulted in a system of two monomers
in AAE and two in AAA conformations.
The geometry of the calculated octamer correlates fairly well
with that of the experimental crystal, except for the dihedrals,
some of which are reported in Table 1, where the values were
averaged among the eight molecules in order to simplify the
analysis. With respect to the monomer and dimer, the most
pronounced difference is found in the N3-C3-N1-N4 dihedral
angle, related to an axial NO2 group in the calculated octamer.
Compared to the value in the crystal, in the AAE monomer
and the dimer this angle is higher by around 20 whereas in
the octamer it is below the crystal value just by 7. Also, in the
three molecules the C-H bonds are longer than the solid-state
values.
In Figure 6 we compare the calculated dimer spectrum with
those of the AAE monomer and tetramer in order to understand
the role of intermolecular interactions on the various modes.
The main modes of monomer, dimer, and tetramer spectra
coincide in position, over all the range (0-3500 cm-1), but some
enhancements in intensities are observed in the dimer and
tetramer, respectively. Also, in the tetramer spectrum there are
two bands near 3200 cm-1 instead of three found in the
monomer and dimer; this difference may be due to the AAA
contributions to the tetramer.
Additional differences emerge when the 0-150 cm-1 region
is amplified, with the most remarkable peak at 17.3 cm-1 which
is attributed to an external vibrational mode (symmetric optical
rotation (OR) through an axis between both molecules), as
shown in Figure 7. In the tetramer, an extra band arises at 43.3
cm-1 which is assigned to an OR of two AAA-RDX molecules
in the tetramer.
3.3. Calculated RDX Dimer and Tetramer versus Poly-
crystalline Experimental Terahertz Spectra. Comparison
between experimental crystal12 and the calculated dimer and
tetramer spectra (Figure 8) shows some correlation between
bands. The experimental spectrum shows no bands equivalent
to those of the calculated dimer at 10.9 and 17.3 cm-1 assigned
to optical rotation of molecules, and on the basis of the results
for the tetramer it could be suggested that as the intermolecular
2288 J. Phys. Chem. A, Vol. 114, No. 6, 2010
Figure 8. RDX terahertz experimental spectrum at 7 K12 (blue), calculated dimer (red), and tetramer (green) spectra.
TABLE 2: Spectral Modes and Assignments for Calculated
RDX Dimer and Tetramer (in italics) and Experimental
Crystalline RDX (in parentheses)12
calculated (experimental) type of motion
33.9, 20.5 (33), 28.7 (41), 43.3 (50) OR
40.7, 54.4 (59), 55.9, 65.3 (73) OR + NO2 bending
49.9, 49.1 (54), 64.5, 65.4 (74), 112.1, OR + NO2 libration
107.5 (116) 98.5, 94.4 (100), 106.8,
94.9 (103), 120.7, 107.13 (121)
67.9, 76.3 (83) OR + all NO2 bending
69.5, 78.8 (85) OT + NO2 libration +
NO2 bending
interactions increase, the bands in this range tend to blue-shift
toward the experimental bands (as shown by the arrow).
In the calculated spectra, bands at 33.9 and 51.9 cm-1 (dimer)
and 20.5 and 43.3 cm-1 (tetramer) correspond to optical rotations
in the molecule equivalent to those at 33 and 54 cm-1 in the
experimental spectra. Another band at 59.6 cm-1 in the dimer,
65.3 cm-1 in the tetramer (73 cm-1 in experimental), accounts
for ring optical rotation and NO2 bending vibrations. Several
bands are due to optical rotations plus NO2 libration, as shown
in Table 2.
3.4. Comparison of AAA Conformer and AAA-Al16
Complex. Figure 9 displays the calculated geometry of RDX
attached to the model Al surface. Although AAE is the most
stable configuration in gas and solid phases, the calculations
indicate that when attached to a layer of Al16, RDX changes to
a more stable geometry where all three NO2 groups locate in
axial-like positions similar to those in the AAA conformer.
Table 3 illustrates that while there is little difference in C-H
distances, a remarkable distinction between the AAA conformer
and AAA-Al16 systems is the geometry of N4. In the complex
this N is in a tetrahedral geometry (N1-N4-O average angle
) 104.4), and in the free molecule it is involved in a more
planar geometry (N1-N4-O ) 116.4 for the AAA conformer).
All N-N bond distances are approximately the same in the
AAE and AAA monomers while in the complex the N1-N4
bond distance is longer because of electron transfer between
N4 and the Al layer, and the other two NN distances are shorter.
Guadarrama-Perez et al.
Also, all the N-O bond distances are the same in the AAE and
AAA monomers while in the complex the N4-O1 and N4-O2
bonds are longer because of O coordination to Al. N6-O6 also
is elongated because of coordination.
The geometry related to the N atoms in the cycle (N1,
N2, and N3) provides information about the NO2 positions.
Dihedrals and angles around N1, N2, and N3 are good
indicators of the variation of the NO2 groups from an axial
position. Similarly, the angle between three consecutive atoms
in the cycle C1, C2, C3 and that of an axial substituent
bonded to the central atom (i.e., C2-H) may also illustrate
the deviation of the substituents from an axial position. In
the AAA-Al16 complex, the NO2 group attached to Al is
nearer to an axial position compared to the free molecule,
as can be seen by a smaller value of the N2-C1-N1-N4
dihedral in AAA-Al16 than both RDX free conformers but
closer to that of the AAA conformer. The NO2 attached to
N3 also interacts with Al16, changing the molecular geometry,
and the C2-N3-N6 angle is 117.16, intermediate between
those of the AAE and AAA monomers.
Resonance plays an important role in N and NO2 geometries.
When NO2 is free, electrons are in resonance through the N-NO2
moiety making the group R-N1-R (Figure 2) close to coplanar
with the NO2 group. The N-NO2 moiety has three resonating
structures:
Since there are two resonance structures with a free
electron pair, the N atom from the nitro group (N4, Figure
5) is expected to be involved in a trigonal planar structure
and the other nitrogen (N1), to form a pyramidal moiety.
When RDX attaches to the Al surface, N4-Al bond
formation breaks the resonance and nonbonding N1 electrons
become available causing the C1-N1-N4 to be smaller
(114.67). This small change in N1 geometry moves its NO2
Spectra of an RDX/Aluminum Complex J. Phys. Chem. A, Vol. 114, No. 6, 2010 2289

Figure 9. Side (a) and top (b) views of RDX molecule attached to Al16. Blue, red, purple, brown, and pink, correspond to Al, O, N, C, and H
atoms, respectively. In the side view, Al-O interactions are shown as dashed lines.

TABLE 3: Geometric Parameters, Bond Distances (),

Angles (deg), and Dihedrals (deg) for AAA-Al16, AAE, and similarities, marked differences are shown in the 0 to 500
AAA Conformers, Calculated at B3LYP/6-311G(d,p) Level cm-1 zone; these are displayed in Figure 11, together with
of Theory the corresponding modes of Al16.
parameter AAE AAA-Al16 AAA
All modes calculated for Al16 correspond to in-plane
vibrations (Al atoms were arranged in a plane, emulating
N1-N4 1.40 1.47 1.42 the top layer of an fcc (111) surface) while in Al16-RDX
N2-N5 1.43 1.38 1.42 in-plane vibrations can only be seen for peaks at 311.5 and
N3-N6 1.43 1.38 1.42
N4-O1 1.22 1.46 1.22 343.4 cm-1. However, the band at 343.4 cm-1 for Al16-RDX
N4-O2 1.22 1.38 1.22 results from in-plane Al atoms vibration-coupled to RDX
N5-O3 1.21 1.22 1.22 optical rotation. This band shows a blue shift with respect
N5-O4 1.21 1.23 1.22 to the one at 327.3 cm-1 in Al16, due to Al in-plane vibrations.
N6-O5 1.21 1.23 1.22 Also, in Al16-RDX, pure ring twisting is present in the last
N6-O6 1.21 1.28 1.22 three vibrations (421.1, 440.7, and 461.4 cm-1), and ring
O1-Al1 2.39 twisting and other kinds of motion (for example NO2
O1-Al2 1.97
O2-Al2 2.67 libration) are present in several bands excluding those at
O2-Al5 1.97 311.5 and 343.4 cm-1.
O6-Al3 2.11 Contrastingly, while the peak at 169.5 cm-1 for Al16
C1-H1ec 1.08 1.08 1.08 corresponds to an in-plane vibration of Al atoms, in
C1-H1ax 1.10 1.09 1.09 AAA-Al16 the peak at 163.3 cm-1 involves out-of-plane
C3-H3ec 1.08 1.08 1.08 vibration (in the z-direction) of Al atoms plus ring torsion.
C1-N1-N4 115.69 114.67 118.03
Correlation was found for bands at 203.4 cm-1 (Al out-of-
C2-N2-N5 116.85 120.51 118.13
C2-N3-N6 116.85 117.16 118.06 plane vibration-coupled to RDX ring twisting and to a NO2
N1-N4-O1 116.6 103.9 116.4 librational mode) and 223.9 cm-1 (Al out-of-plane vibration-
N1-N4-O2 116.6 104.9 116.4 coupled to ring twisting) in AAA-Al16, with the band at
N2-C1-N1-N4 166.23 89.08 -102.90 216.5 cm-1 in the AAA monomer (ring twisting). As seen
N2-C2-N3-N6 95.94 125.78 102.86 previously, in Al16 no peaks were the result of out-of-plane
N3-C2-N2-N5 -95.94 -99.61 -103.24 vibrations. For AAA-Al16, NO2 librational modes are implied
in those vibrations in the range from 67.4 to 203.4 cm-1,
group toward the center of the cycle and makes 1,3-diaxial except for the band at 163.3 cm-1.
interactions more important, pushing the other two nitro Unexpectedly, the strongest vibration calculated in Al16
groups away from the center of the cycle, which is reflected corresponding to an in-plane vibration at 268.6 cm-1 does
in AAA-Al16: new, larger C2-N2-N5 and C2-N3-N6 not exactly match the same motion found in the strongest
angle values than in the AAE conformer. band for the Al16-RDX complex located at 272.2 cm-1 which
In AAA-Al16, the most planar fragment involving a nitrogen is due to Al in-plane vibrations with some contribution in
is C2-N2-N5 (bonded to a non Al interacting NO2, Figure the z direction plus RDX optical rotation. As it can be seen
9), shown by a C2-N2-N5 angle value near 120 and a in Figure 12, displacement vectors corresponding to such
N2-C2-N3-N6 dihedral value of about 125.78. O1 and O2 modes are randomly oriented.
seem to be in bridge positions over the Al layer. N4 is also Very interesting changes are also observed in the mid-IR
close enough to Al4 to be able to develop an interaction and region, which are summarized in Table 4. The main differences
become tetrahedral. observed between the two spectra are as follows:
In order to understand Al16-RDX behavior and to find if (a) Greater intensity of the AAA-Al16 peak at 563.03 cm-1.
there is any correlation between bands of the monomer and This peak corresponds to an inversion angle of the N6 (Figure
the adsorbed molecule, the IR spectra of the calculated AAA 9) in the NO2 group. In the AAA conformer spectrum this peak
monomer (red) and Al16-RDX (black) are plotted simulta- is not observed; instead there is one peak at 592.52 cm-1
neously in Figures 10 and 11. Although there are many corresponding to CH2 rocking.
2290 J. Phys. Chem. A, Vol. 114, No. 6, 2010 Guadarrama-Perez et al.

Figure 10. IR spectra of AAA-RDX monomer (red) and RDX-Al16 (black) calculated at B3LYP/6-311G(d,p) level.

Figure 11. AAA monomer (red), RDX-Al16 (black), and Al16 (blue) IR calculated spectra (0-500 cm-1).

Figure 12. Displacement vectors for vibrations of aluminum atoms in (a) Al16 and (b) AAA-Al16.

(b) The AAA monomer does not have peaks between 784.44 with respect to the free AAA monomer is an asymmetrical
and 890.92 cm-1 whereas four peaks at 794.62, 826.19, 852.23, stretching in the NO2 group bonded to the Al surface.
and 885.50-1 cm are observed in the AAA-Al16 system. The (c) There is a big peak at 1677.5 cm-1 for the AAA monomer,
only difference in the modes corresponding to these four peaks corresponding to NO2 asymmetrical stretching, whereas a red-
Spectra of an RDX/Aluminum Complex J. Phys. Chem. A, Vol. 114, No. 6, 2010 2291

TABLE 4: Calculated Vibrational Modes in the Mid-IR Range for the AAA Conformer and the AAA-Al16 Complex
AAA
frequency
(cm-1) AAA conformer mode AAA-Al16 frequency (cm-1) AAA-Al16 mode
592.52 CH2 rocking 563.03 inversion angle NO2 (N6, Figure 9)
663.14 CN2 scissoring 578.02 NO2 scissoring
CH2 rocking
784.44 CN2 and NO2 scissoring 767.29 CN2 and NO2 scissoring
CH2 rocking NO2 asymmetrical stretching (N4, Figure 9)
890.92 NC2 scissoring 794.62 NO2 scissoring CH2 rocking
NO2 symmetrical stretching NO2 asymmetrical stretching (N4, Figure 9)
912.62 CH2 rocking 826.19 NO2 scissoring
CN2 asymmetrical stretching CN2 asymmetrical stretching
939.54 CH2 rocking 852.23 NO2 scissoring (N4, Figure 9)
CN2 symmetrical stretching CN2 asymmetrical stretching
NO2 asymmetrical stretching (N4, Figure 9)
1009.52 CH2 rocking 885.50 CH2 rocking
CH2 twisting NC2 and NO2 symmetrical stretching
1255.66 NC2 asymmetrical stretching 926.97 CH2 rocking
CN2 asymmetrical stretching
NO2 symmetrical stretching
1296.36 CH2 wagging 946.66 CH2 rocking
NO2 symmetrical stretching NO2 symmetrical stretching
1351.85 CH2 scissoring 1013.17 CH2 rocking
NO2 symmetrical stretching
1400.96 CH2 wagging 1252.07 CH2 rocking
NO2 symmetrical stretching NC2 asymmetrical stretching
1482.32 CH2 scissoring 1308.71 CH2 wagging
NO2 symmetrical stretching
1677.50 NO2 asymmetrical stretching 1356.64 CH2 wagging and twisting
1406.75 CH2 wagging
NO2 symmetrical stretching
1482.55 CH2 scissoring
1603.47 NO2 asymmetrical stretching

shifted peak at 1603.47 is observed for the AAA-Al16 system
related to the NO2 asymmetrical stretching.
(d) The last peak in this region is observed at 1677.5 cm-1
for the AAA conformer (corresponding to NO2 asymmetrical
stretching). In the AAA-Al16 complex this same peak is again
red-shifted at 1603.47 cm-1.
3.5. AAA-Al16 Complex versus Experimental RDX over
Aluminum Surface. A comparison between the terahertz
spectra of RDX experimentally crystallized over an Al plate
and that calculated for the AAA-Al16 model complex is shown
in Figure 13. In order to simulate terahertz experimental
observations, the full width at half-maximum of each calculated
peak was set to 3 cm-1.
The assignments and correspondence among modes are
reported in Table 5. The group of bands near 20 cm-1 in the
experimental spectrum may be assigned to intermolecular
RDX-RDX interactions, where optical translations and rotations
should be observed as inferred from the calculated dimer modes
discussed in relation to Figure 8. Other assignments reveal
coupling of the molecular motions to those of the atoms of the
substrate.
We note that this work is only a first attempt to interpret this
complex spectrum. In the experiments of ref 10 a polycrystalline
RDX thin film is deposited on a metal surface; thus, our
simulated system lacks the RDX-RDX intermolecular interac-
tions. In addition, our simplified model for the Al surface may

Figure 13. Overlap of terahertz and IR spectra of AAA-Al16 (red) and that of experimental RDX crystallized over an Al plate (blue).10
2292 J. Phys. Chem. A, Vol. 114, No. 6, 2010
TABLE 5: Spectral Modes and Assignments for Calculated
AAA-Al16 and Experimental RDX Crystallized over an
Aluminum Plate10
calculated (experimental) type of motion
31.8 (30.6) out-of-plane Al vibration +
ORa normal to Al layer plane +
NO2 rocking
38.5 (41.7), 43.2 (45.9), out-of-plane Al vibration +
51.5 (52.7), 108.8 (112.9) ORa parallel to Al layer plane
64.5 (71.5) in-plane Al vibration
67.4 (74.9), 78.9 (81.1), out-of-plane Al vibration +
85.4 (85.3), 92.3 (96.4), NO2 libration
105.9 (108.1), 114.3 (118.1)
a
RDX optical rotation.
introduce some artifacts because of its small size and thickness
and the presence of edge effects. However, we consider that
developing a stepwise understanding of the way intermolecular
or lattice modes may be built is a useful approach. We are
currently carrying out density functional theory calculations in
periodic cells, to investigate both molecular and thin film
interactions with the substrate and vibrational modes. We have
also performed classical molecular dynamics simulations of
RDX crystals and thin films. Those will be reported elsewhere.
4. Conclusions
DFT calculations illustrate that differences between the
vibrational spectra of the RDX AAE and AAA monomers in
gas phase are mainly given by higher AAE monomer intensities
for CH2 wagging and N-N bond stretching whereas the modes
corresponding to CH2 rocking are blue-shifted in the AAA
monomer. As intermolecular interactions are built (from mono-
mer to dimer and tetramer), the largest differences are found in
the terahertz and low IR (0-140 cm-1) region of the spectrum,
and they are attributed to symmetric optical rotations between
pair of molecules. Low frequency peaks, found in the range
10-20 cm-1 in the dimer and tetramer, as well as optical
rotations and NO2 bending appear shifted toward higher
intensities in the experimental crystal spectrum. Optical rotations
in the range 30-55 cm-1 for dimer and tetramer agree fairly
well with those of the crystal.
In the RDX-Al16 complex, the RDX molecular geometry is
closer to that of the AAA conformation, with the three NO2
groups in nearly axial positions. However, comparison of the
spectra of the gas-phase AAA monomer, the Al16 surface and
that of the complex yield significant differences. In-plane modes
of Al16 are shifted to higher frequencies in the complex, and
several new coupled modes (Al16-RDX) appear between 200
and 400 cm-1 in the complex. Other differences are revealed
in the mid-IR region of the spectra, where the modes of the
molecule attached to the model aluminum surface are red-shifted
with respect to those in the free molecule because of the
interactions of the NO2 group with the metal atoms.
The comparison of the AAA-Al16 complex with the experi-
mental results of ref 10 yields some similarities, and preliminary
assignments are performed based on them; however, we note
that more elaborate models are needed to achieve a better
interpretation of the complex interactions that may exist between
a polycrystalline RDX film and the metal surface.
Acknowledgment. We gratefully acknowledge financial
support from the US Army Research Office and the US Defense
Threat Reduction Agency (DTRA). Computational resources
Guadarrama-Perez et al.
from TAMU Supercomputer Facility, University of Texas
TACC, and NERSC are also acknowledged.
Supporting Information Available: NBO population analy-
sis of the RDX dimer. This material is available free of charge
via the Internet at http://pubs.acs.org.
References and Notes
(1) Millar, D. I. A.; Oswald, I. D. H.; Francis, D. J.; Marshall, W. G.;
Pulham, C. R.; Cumming, A. S. The crystal structure of beta-RDXsan
elusive form of an explosive revealed. ChemComm 2009, 473, 562564.
(2) McCrone, W. C. Crystallographic Data. 32. RDX (Cyclotrimeth-
ylenetrinitramine). Anal. Chem. 2002, 22, 954955.
(3) Hakey, P.; Ouellette, W.; Zubieta, J.; Korter, T. Redetermination
of cyclo-trimethylenetrinitramine. Acta Crystallogr., Sect. E: Struct. Rep.
Online 2008, 64, o1428.
(4) Ciezak, J. A.; Jenkins, T. A. The Low-Temperature High-Pressure
Phase Diagram of Energetic Materials: I. Hexahydro-1,3,5-Trinitro-s-
Triazine. Propellants, ExplosiVes, Pyrotechnics 2008, 33, 390395.
(5) Davidson, A. J.; Oswald, I. D. H.; Francis, D. J.; Lennie, A. R.;
Marshall, W. G.; Millar, D. I. A.; Pulham, C. R.; Warren, J. E.; Cumming,
A. S. Explosives under pressure-the crystal structure of [gamma]-RDX as
determined by high-pressure X-ray and neutron diffraction. CrystEngComm
2008, 10, 162165.
(6) Vladimiroff, T.; Rice, B. M. Reinvestigation of the Gas-Phase
Structure of RDX Using Density Functional Theory Predictions of Electron-
Scattering Intensities. J. Phys. Chem. A 2002, 106, 1043710443.
(7) Karpowicz, R. J.; Brill, T. B. Comparison of the molecular structure
of hexahydro-1,3,5-trinitro-s-triazine in the vapor, solution and solid phases.
J. Phys. Chem. 1984, 88, 348352.
(8) Boyd, S. G.; Boyd, K. J. A computational analysis of the interaction
of lattice and intramolecular vibrational modes in crystalline alpha-RDX.
J. Chem. Phys. 2008, 129, 134502.
(9) Boyd, S.; Gravelle, M.; Politzer, P. Nonreactive molecular dynamics
force field for crystalline hexahydro-1,3,5-trinitro-1,3,5 triazine. J. Chem.
Phys. 2006, 124, 104508104510.
(10) Melinger, J. S.; Laman, N.; Grischkowsky, D. The underlying
terahertz vibrational spectrum of explosives solids. Appl. Phys. Lett. 2008,
93, 011102.
(11) Rice, B. M.; Chabalowski, C. F. Ab Initio and Nonlocal Density
Functional Study of 1,3,5-Trinitro-s-triazine (RDX) Conformers. J. Phys.
Chem. A 1997, 101, 87208726.
(12) Allis, D. G.; Zeitler, J. A.; Taday, P. F.; Korter, T. M. Theoretical
analysis of the solid-state terahertz spectrum of the high explosive RDX.
Chem. Phys. Lett. 2008, 463, 8489.
(13) Becke, A. D. Density-functional exchange-energy approximation
with correct asymptotic behavior. Phys. ReV. A 1988, 38, 3098.
(14) Becke, A. D. Density-functional thermochemistry. III. The role of
exact exchange. J. Chem. Phys. 1993, 98, 56485652.
(15) Lee, C.; Yang, W.; Parr, R. G. Development of the Colle-Salvetti
correlation-energy formula into a functional of the electron density. Phys.
ReV. B 1988, 37, 785.
(16) Hariharan, P. C.; Pople, J. A. The influence of polarization functions
on molecular orbital hydrogenation energies. Theor. Chem. Acc. 1973, 28,
213222.
(17) Gaussian, Inc. GaussView; 3.0 ed., 2003.
(18) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.;
Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.;
Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.;
Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.;
Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li,
X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.;
Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.;
Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.;
Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich,
S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.;
Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.;
Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz,
P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.;
Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson,
B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03,
Revision D.02, Gaussian, Inc., Wallingford, CT, 2003.
(19) Foster, J. P.; Weinhold, F. Natural hybrid orbitals. J. Am. Chem.
Soc. 2002, 102, 72117218.
(20) Glendening, E. D.; Reed, A. E.; Carpenter, J. E.; Weinhold, F. NBO
Version 3.1.
JP909976D