Infrared line collisional parameters of HCl in argon, beyond the impact approximation: Measurements and classical path calculations

被引:32
作者
Boulet, C [1 ]
Flaud, PM [1 ]
Hartmann, JM [1 ]
机构
[1] Univ Paris 11, Photophys Mol Lab, UPR 3361, CNRS, F-91405 Orsay, France
关键词
D O I
10.1063/1.1714794
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Measurement of room temperature absorption by HCl-Ar mixtures in the 1-0 and 2-0 bands have been made for pressures between 10 and 50 atm. Fits of these spectra are made for the determination of the width, spectral shift, asymmetry, and intensity of individual lines. The broadening and shifting parameters are in satisfactory agreement with previous determinations but provide the first complete and self-consistent sets covering P(15)-R(14) and P(7)-R(8) in the 1-0 and 2-0 bands, respectively. The asymmetries of the profiles, which have been studied for the first time, are smaller than typically 10(-3) atm(-1) and cannot be determined experimentally. On the other hand, the intensities of the low j lines show a significant linear decrease with increasing Ar pressure. Calculations of all measured quantities are made with a classical path approach and an accurate vibrational-dependent HCl-Ar potential energy surface (PES). Comparisons with experimental values show that widths and shifts are well predicted, confirming the quality of the PES and of the theoretical model, and the calculations confirm that asymmetries are small. The damping factors of the intensities are analyzed by considering three contributions: The first is due to the formation of van der Waals complexes, the second results from the finite duration of collisions, and the last comes from initial correlations. Calculations indicate that the last process has negligible consequences but that the first two processes lead to effects of the same order and explain most of the observed decrease of the intensities, even if some discrepancies persist for the \m\=1 rotational components. (C) 2004 American Institute of Physics.
引用
收藏
页码:11053 / 11061
页数:9
相关论文
共 36 条
[1]  
ATWOOD M, 1967, CR HEBD ACAD SCI, V264, P1903
[2]   SPECTROSCOPY AND THERMODYNAMICS OF ARHCL [J].
BERNSTEIN, LS ;
WORMHOUDT, J .
JOURNAL OF CHEMICAL PHYSICS, 1984, 80 (10) :4630-4639
[3]   Ab initio line shape cross sections:: On the need of off-the-energy shell calculation [J].
Boissoles, J ;
Boulet, C ;
Bruet, X .
JOURNAL OF CHEMICAL PHYSICS, 2002, 116 (17) :7537-7543
[4]   Spectral lineshape parameters revisited for HF in a bath of argon - II. Asymmetries in the (0-0), (0-1), and (0-2) bands [J].
Boissoles, J ;
Thibault, F ;
Boulet, C ;
Bouanich, JP ;
Hartmann, JM .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1999, 198 (02) :257-262
[5]   INFLUENCE OF BOUNDED TRAJECTORIES IN THE STUDY OF BINARY TIME CORRELATION-FUNCTIONS [J].
BONAMY, L ;
HOANG, NM .
JOURNAL OF CHEMICAL PHYSICS, 1980, 72 (01) :741-750
[6]   NOBLE-GAS BROADENING OF VIBRATION-ROTATION LINES BELONGING TO DIATOMIC-MOLECULES .2. THEORETICAL CALCULATIONS OF HCL LINESHIFTS AND WIDTHS [J].
BOULET, C ;
ISNARD, P ;
LEVY, A .
JOURNAL OF QUANTITATIVE SPECTROSCOPY & RADIATIVE TRANSFER, 1973, 13 (09) :897-909
[7]   Non-adiabatic approach to the asymmetry of pressure broadened spectral lines [J].
Ciurylo, R ;
Szudy, J ;
Trawinski, RS .
JOURNAL OF QUANTITATIVE SPECTROSCOPY & RADIATIVE TRANSFER, 1997, 57 (04) :551-557
[8]   DIPOLE AUTO-CORRELATION FUNCTION FOR MOLECULAR PRESSURE BROADENING - A QUANTUM-THEORY WHICH SATISFIES THE FLUCTUATION-DISSIPATION THEOREM [J].
DAVIES, RW ;
TIPPING, RH ;
CLOUGH, SA .
PHYSICAL REVIEW A, 1982, 26 (06) :3378-3394
[9]   THEORETICAL LINE-SHAPES FOR ROTATIONAL SPECTRA OF HCL IN AR [J].
GREEN, S .
JOURNAL OF CHEMICAL PHYSICS, 1990, 92 (08) :4679-4685
[10]   MEASUREMENTS OF PRESSURE-INDUCED SHIFTS IN 1-0 AND 2-0 BANDS OF HF AND IN 2-0 BANDS OF HCL-35 AND HCL-37 [J].
GUELACHVILI, G ;
SMITH, MAH .
JOURNAL OF QUANTITATIVE SPECTROSCOPY & RADIATIVE TRANSFER, 1978, 20 (01) :35-47