Semiclassical calculations with exact trajectory for N-2 rovibrational Raman linewidths at temperatures below 300 K

A new model of exact-trajectory semiclassical calculations proposed by Byko v et al. (Atmos Oceanic Opt 1992;5:728) for electrostatic resonance functio ns is generalized to the case of short-range interactions in the form of at om-atom potential by the help of two-centre expansion. For the first time, explicit expressions are applied to practical calculations of experimentall y measured N-2 rovibrational Raman linewidths. Two traditional models of st raight-line and parabolic trajectories are also involved in calculations to trace the evolution due to the complication of the trajectory. Thorough co mparative analysis is fulfilled for low (113 K) and ordinary (298 K) temper ature resonance functions of exact and parabolic trajectory models and sign ificant role of better path description for linewidths (in the range of sem iclassical approach validity) is demonstrated. (C) 1999 Elsevier Science Lt d. All rights reserved.