Collisional transition probability and nonequilibrium unimolecular rate
Abstract
The paper examines six models for the collisional transition probability between energy levels in polyatomic reactant molecules for a unimolecular reaction at the lowpressure limit under nonequilibrium (weakcollision) conditions. These models are (1) exponential, (2) bimodal Gaussian, (3) unimodal Gaussian, (4) bimodal gamma, (5) unimodal gamma, and (6) SchwartzSlawskyHerzfeld models. Results of calculations are presented for three models representing collisional activation in hydrogen peroxide and for several models representing collisional activation in methyl isocyanide. When compared at the same average energy transferred per deactivating collision, the various models yield results for the ratio of nonequilibrium to equilibrium rate constant and the difference between equilibrium and nonequilibrium activation energy that are virtually indistinguishable experimentally.
 Publication:

In: International Symposium on Combustion
 Pub Date:
 1975
 Bibcode:
 1975comb.symp..681B
 Keywords:

 Activation Energy;
 Chemical Equilibrium;
 Energy Transfer;
 Molecular Collisions;
 Reaction Kinetics;
 Transition Probabilities;
 Nonequilibrium Conditions;
 Atomic and Molecular Physics