Nonperturbative analytic theory of V-T and V-V rates in diatomic gases, including multi-quantum transitions

摘要

The paper addresses the analysis, validation, and application of analytic, nonperturbative, semiclassical vibration-translation (V-T) and vibration-vibration-translation (V-V-T) rate models for atom-diatom and diatom-diatom vibrational molecular energy transfer collisions. These "forced harmonic oscillator" (FHO) rate models are corrected and validated by comparison with recent experiments, and with three-dimensional semiclassical trajectory calculations for N_2-N_2, O_2-O_2, and N_2-O_2, which are considered to be the most reliable theoretical data available. A remarkably good overall agreement is shown, for both the temperature and quantum number dependence of single-quantum and double-quantum V-V-T transitions in the temperature range 200<=T<=8000 K and for vibrational quantum numbers 0<=v<=40.