Collisional broadening of rotationndash;vibration lines for asymmetric top molecules. I. Theoretical model for both distant and close collisions

摘要

A semiclassical theory of infrared linewidths in the gas, previously developed for linear molecules, is extended to asymmetric top molecules. It includes a satisfactory treatment of the close collisions and is consequently adapted to describe the temperature dependence of the linewidths, in particular in the combustion temperature range. Numerical applications to the water vapor perturbed by nitrogen, oxygen, and argon show strong different behaviors following the nature of the perturber. For oxygen and argon perturbers, the contribution of close collisions is the predominant mechanism of line broadening. The consistency of the theoretical model is evidenced by comparison with precise measurements for H2Ondash;N2, ndash;O2, and Ar at 300 K. Moreover, the calculated temperature dependence of the linewidths is compared with recent experimental data for H2Ondash;Ar between 1300 and 2300 K.