Theoretical study of VRT energy transfer in Ne + I2(B) collisions using a spectroscopic interaction potential

Abstract

A theoretical analysis of the Ne + I₂(B) inelastic collision dynamics is performed as an example of reliable and detailed calculations of microscopic rate constants. Very good agreement with the available experimental data is achieved using an empirical interaction potential determined from spectroscopic and dynamical data for the Ne···I₂(B) van der Waals complex. Classical, semiclassical and quantum methods for calculating state-resolved collision cross sections and rate constants are compared. The quasiclassical trajectory approach is found to be efficient and reliable, whereas special care in the approximate separation of quantum and classical degrees of freedom is necessary to implement correctly the semiclassical method. The theoretical results are used to check the validity of some scaling laws for vibrational–rotational energy transfer in atom–diatom collisions.