N 2- and O 2-broadening coefficients of C 2H 2 IR lines

Abstract

Pressure-broadening parameters of six lines belonging to the ν 5 band of C 2H 2 in collision with N 2 have been measured with a tunable diode-laser spectrometer in order to complete up to J = 33 our earlier measurements (D. Lambot, G. Blanquet, and J. P. Bouanich, J. Mol. Spectrosc. 136, 86–92 (1989)) on the broadening of C 2H 2 by N 2 and O 2 at 297 K. These N 2- and O 2-broadening coefficients have been first calculated on the basis of the Anderson-Tsao-Curnutte theory; in this approach, we show that the short-range interactions which contribute significantly to the linewidths are not correctly treated. Next, we consider the improved semiclassical model proposed by Robert and Bonamy. The intermolecular potential consists in the addition of the atom-atom interaction model to the quadrupolar interactions. The limited radial spherical harmonics expansion of the atom-atom potential, from which expressions for the differential cross section were derived, appears to be quite insufficient at short intermolecular distances. Therefore, we use a more accurate representation of this potential, avoiding an inadequate truncation and keeping the analytic expressions obtained by Bonamy and Robert. In the calculations we take into account the contributions derived from the radial functions U 000( r), U 200( r), and U 220( r), as well as from U 400( r). A theoretical expression is obtained for the U 400 contribution to the differential cross section. The results of the calculations arising from the exact radial expansion of the atom-atom potential appear to be significantly larger for high J lines than those arising from the truncated expansion. The latter results, which do not include adjustable atom-atom parameters, are in good agreement with experimental broadening coefficients for C 2H 2O 2 and in reasonable agreement (except at large J values) for C 2H 2N 2. It is also shown that the contributions to the linewidths derived from U 400 are rather small for C 2H 2N 2 and more important for C 2H 2O 2. Finally, by calculating the collisional linewidths of C 2H 2N 2 and C 2H 2O 2 at 200 K, we have predicted their temperature dependences.