Stochastic Model of Unimolecular Reactions and the RRKM Theory

S H Lin; K H Lau; W Richardson; L Volk; H Eyring

doi:10.1073/pnas.69.10.2778

. 1972 Oct;69(10):2778–2782. doi: 10.1073/pnas.69.10.2778

Stochastic Model of Unimolecular Reactions and the RRKM Theory

S H Lin ^*, K H Lau ^*, W Richardson ^*, L Volk ^*, H Eyring ^†

PMCID: PMC389643 PMID: 16592018

Abstract

A stochastic model of unimolecular reactions has been adopted for investigation of the validity and limitation of the RRKM theory. The error caused by the steady-state approximation for distribution of energized molecules is small, while the assumption of the internal energy equilibration of energized molecules might cause serious errors for reactions of low activation energies.

Keywords: steady-state approximation, energized molecules