Journal of Molecular Spectroscopy 235 (2006) 265267 www.elsevier.

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Note

Improved ground state rotational parameters of deuterium uoride, DF

Gabriele Cazzoli a,*, Cristina Puzzarini a, Filippo Tamassia b, Simone Borri c,d, Saverio Bartalini c,d
c a ` di Bologna, Via Selmi 2, I-40126 Bologna, Italy Dipartimento di Chimica G. Ciamician, Universita ` di Bologna, V.le Risorgimento 4, I-40136 Bologna, Italy Dipartimento di Chimica Fisica ed Inorganica, Universita ` di Firenze, and Laboratorio Europoeo Spettroscopia Non-Lineare (LENS), Via Nello Carrara 1, Dipartimento di Fisica, Universita I-50019 Sesto F.no (FI), Italy d Istituto Nazionale di Ottica Applicata (INOA), Largo E. Fermi 6, I-50125 Firenze, Italy b

Received 9 September 2005 Available online 27 December 2005

Abstract The rotational spectrum of DF in the 1.33.3 THz frequency region has been observed by means of a tunable far-infrared spectrometer. The J + 1 J, with J = 14, rotational transitions of DF have been recorded with an accuracy of the order of 50200 kHz. These measurements, in conjunction with the hyperne components of the J = 1 0 transition recently observed [Cazzoli and Puzzarini, J. Mol. Spectrosc. 231 (2005) 124130] and the rotational transitions up to J = 47 [R.S. Ram, Z. Morbi, B. Guo, K.-Q. Zhang, P.F. Bernath, J. Vander Auwera, J.W.C. Johns, S.P. Davies, Astrophys. J. Suppl. Series 103 (1996) 247254] consented to improve the ground state rotational parameters of DF. 2005 Elsevier Inc. All rights reserved.
Keywords: Rotational spectrum; Rotational parameters; Deuterium uoride; TuFIR

As outlined in [1], an improvement in the knowledge of the spectroscopic parameters of DF could be useful to astrophysical purposes. In fact, as highlighted in [2], the HF molecule is the most convenient monitor of 19F abundances in cool stars and HF is practically the only F containing molecule found in extraterrestrial sources. Additionally, the [D]/[H] ratio in the interstellar medium is of great interest. Very recently the hyperne structure due to the deuterium and uorine nuclei of the J = 1 0 transition of DF has been completely resolved employing the Lamb-dip technique [1]. These measurements, together with the rotational transitions of [2] provided the most accurate ground state rotational constants to date [1]. Nevertheless, the spectroscopic parameters of DF can be further improved since, with the exception of the J = 1 0 transition, the pure rotational data available are aected by a rather large uncer*

Corresponding author. Fax: +39 051 209 9456. E-mail address: gabriele.cazzoli@unibo.it (G. Cazzoli).

tainty (about 15 MHz). This is the reason why we decided to re-investigate some lowJ transitions (J + 1 J, J = 14) in the far-infrared region between 1.3 and 3.3 THz. These measurements were recorded with an accuracy ranging roughly from 50 to 200 kHz. The spectra have been recorded with a tunable far-IR spectrometer (TuFIR), described into details in [3,4], operating at LENS (European Laboratory for Nonlinear spectroscopy). Briey, the far-IR (FIR) radiation is generated employing a third-order mixing; that is, two xed frequency stabilized CO2 lasers and a tunable microwave component are coupled by means of a MetalInsulatorMetal (MIM) diode. Then the far-IR radiation passes through the absorption cell, a pyrex tube 80 cm long equipped with high-density polyethylene windows, and is detected by a composite SiDiamond bolometer cooled at 1.4 K. The FIR radiation is sine wave modulated at a frequency of 1.2 kHz with a amplitude in the range 0.51.1 MHz, depending on the transition under consideration as well as other experimental conditions, and the resulting FIR signal is the rst derivative of the natural

0022-2852/$ - see front matter 2005 Elsevier Inc. All rights reserved. doi:10.1016/j.jms.2005.11.005

266 Table 1 Rotational transitions of DF J0 1 1 1 1 1 1 1 1 1 2 3 4 5 J0 6 7 8 9 13 14 15 16 17 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48

a b c

G. Cazzoli et al. / Journal of Molecular Spectroscopy 235 (2006) 265267

F 01 0 0 2 2 2 1 1 1 1

F0 1/2 1/2 3/2 3/2 5/2 1/2 1/2 3/2 3/2

J00 0 0 0 0 0 0 0 0 0 1 2 3 4 J00 5 6 7 8 12 13 14 15 16 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47

F 00 1 1 1 1 1 1 1 1 1 1

F 00 1/2 3/2 o 3/2 1/2 3/2 o 3/2 1/2 o 1/2 3/2 o

Observed freq. (MHz) 651099.2774(7)

a

o c (kHz) 0.08 0.02 0.33 0.03 0.00 44.6 208.1 30.6 23.0 o c (MHz) 0.3 0.7 0.4 2.5 42.6 19.5 14.9 27.6 38.0 1.2 19.6 11.3 5.2 3.2 2.0 1.6 1.3 1.2 2.1 4.6 3.5 10.3 4.7 8.7 4.7 0.2 11.2 5.1 7.9 15.2 7.1 3.0 4.9 9.7 18.5 9.5 24.8 2.9 4.8

651099.3016(5)a 651099.5416(11)a 651099.5571(5)a 651099.6361(1)a 1301776.459(196)b 1951608.972(212)b 2600175.552(193)b 3247057.191(48)b Observed freq.c (MHz) 3891836.7(150) 4534098.9(150) 5173431.2(150) 5809428.3(150) 8312055.3(150) 8925370.1(150) 9533015.5(150) 10134619.3(150) 10729797.8(150) 11899406.0(150) 12473176.7(150) 13039171.1(150) 13597036.0(150) 14146453.9(150) 14687121.8(150) 15218742.3(150) 15741031.1(150) 16253702.0(150) 16756493.8(150) 17249153.9(150) 17731418.3(150) 18203064.4(150) 18663843.6(150) 19113559.6(150) 19551986.8(150) 19978934.5(150) 20394210.0(150) 20797658.7(150) 21189087.2(150) 21568342.4(150) 21935296.7(150) 22289798.9(150) 22631710.7(150) 22960925.1(150) 23277334.1(150) 23580816.7(150) 23871275.2(150) 24148710.3(150) 24412979.8(150)

Ref. [1]. This work. Ref. [2].

line prole. Spectra have been observed in the range 1.3 3.3 THz and, for a given J transition, a set of measurements has been carried out.

Deuterium uoride has been synthesized by mixing HF and D2O vapors in the ratio 2:1 directly in the absorption cell. The isotopic H/D exchange was ecient enough to

G. Cazzoli et al. / Journal of Molecular Spectroscopy 235 (2006) 265267 Table 2 Spectroscopic constants of DF This worka B0 (MHz) D0 (MHz) H0 (kHz) L0 (Hz) M0 (mHz) eQq (D) (MHz) CI (D) (kHz) CI (F) (MHz) S12 (kHz) r (MHz) v2
a b c d

267

This workb 325584.96176(26) 17.611905(92) 0.71428(16) 0.03443(10) 0.001285(22) 0.3544(21) 5.62(38) 0.15784(60) 21.9(8) 11.2 0.83

Cazzoli and Puzzarini (2005)c 325584.96077(62) 17.611420(300) 0.71360(44) 0.03410(22) 0.001229(39) 0.3535(30) 5.755xed 0.15803(80) 21.4(13) 10.3 0.79

Cazzoli and Puzzarini (2005)d 325584.96078(63) 17.611420(300) 0.71360(44) 0.03410(23) 0.001229(40) 0.3544(35) 5.62(30) 0.15784(90) 21.9(17) 10.4 0.79

325584.96171(21) 17.611903(91) 0.71428(16) 0.03443(10) 0.001284(21) 0.3544(20) 5.755xed 0.15775(54) 21.7(7) 11.1 0.83

Results from the rst t. See text. Results from the second t. See text. Ref. [1]: rst column of Table 2. Ref. [1]: second column of Table 2.

produce an amount of DF detectable with a good signalto-noise ratio. The pressure ranged between 50 and 300 mTorr, depending on the strength of the transition and on the FIR power. Since the rst derivative of the absorption lines has actually been recorded, a line prole analysis has been performed in order to retrieve the transition frequencies. In particular, experimental line proles have been tted to the rst derivative of a gaussian function. The retrieved frequencies, reported in Table 1, have been obtained as averages of a set of measurements, and one standard deviation (1r) has been taken as uncertainty aecting our measurements. Following what has been done in [1], dierent ts have been performed. They have been carried out with Picketts SPCAT/SPFIT program [5], and they are least-squares ts in which each line is weighted proportionally to the inverse square of its experimental uncertainty. The second and third ts of [1] have been repeated including the new frequencies values. In both ts, the transition frequencies obtained in the present investigation have been added to those from [1,2]. In the rst t, all the parameters but CI (D) have been tted. The residuals (o c) obtained are given in Table 1. In the second t, the CI (D) constant has also been determined. In this case, since there are 5 hyperne components frequencies available and 5 determinable hyperne parameters, these can be evaluated with their standard error, but the 5 hyperne components of the J = 1 0 transition have been reproduced without errors. Both ts are reported in Table 2, where they are compared with those from [1]. The new parameters show a good agreement with those of [1] and, as expected, their uncertainties were reduced in this work. Also the accuracy of the hyperne constants has been slightly improved. As already noticed in [1], both ts provide a value of the di-

mensionless standard error v2 < 1:0, which means that on average they are able to reproduce the observed frequencies with dierences lower than the experimental uncertainties. It is interesting to point out that the transition frequencies of this work are in very good agreement with the predicted frequencies from [1], and consequently residuals for these transitions have been largely reduced, as can be observed from the comparison between Table 1 of [1] and Table 1 of the this note. In conclusion, the measurements of the J + 1 J, with J = 14, rotational transitions of DF, recorded with an accuracy of about 50200 kHz, allowed us to further improve the ground state rotational parameters with respect to [1]. Acknowledgments This work was supported by MIUR (ex-40%), CNR and University of Bologna (funds for selected research topics and ex-60% funds). The authors thank the European Laboratory for Nonlinear Spectroscopy (LENS) for the opportunity of using their Tu-FIR spectrometer and for technical support. References
[1] G. Cazzoli, C. Puzzarini, J. Mol. Spectrosc. 231 (2005) 124130. [2] R.S. Ram, Z. Morbi, B. Guo, K.-Q. Zhang, P.F. Bernath, J. Vander Auwera, J.W.C. Johns, S.P. Davies, Astrophys. J. Suppl. Ser. 103 (1996) 247254. [3] L.R. Zink, P. De Natale, F.S. Pavone, M. Prevedelli, K.M. Evenson, M. Inguscio, J. Mol. Spectrosc. 143 (1990) 304310. [4] F.S. Pavone, L.R. Zink, M. Prevedelli, M. Inguscio, L. Fusina, J. Mol. Spectrosc. 144 (1990) 4550. [5] H.M. Pickett, J. Mol. Spectrosc. 148 (1991) 371377.