Application of state-to-state approach in estimation of thermally nonequilibrium reaction rate constants in mode approximation

A model to calculate nonequilibrium factor and vibrational energy lost by molecules of reagents and energy released into vibrations of product molecules in the course of chemical reactions under two-temperature approximation is suggested. The model is based on the summation of level rate constants, utilizes simple physical suppositions and does not contain any semiempirical parameters. The model demonstrates a good agreement with data on dissociation and exchange reactions obtained by using quasiclassical trajectory calculations. Then a comparison with some popular two-temperature models is performed. The developed model exhibits better versatility and coincidence with the results of QCT calculations. (C) 2011 Elsevier B.V. All rights reserved.