A transition state theorybased statistical distribution of unimolecular decay rates with application to unimolecular decomposition of formaldehyde
Abstract
A statistical distribution of statespecific unimolecular decay rates is derived (within the framework of random matrix theory) that is determined completely by the transition state properties of the potential energy surface. It includes the standard χsquare distributions as a special case. Model calculations are presented to show the extent to which it can differ from the χsquare distribution, and specific application is made to the statespecific unimolecular decay rate data for D_{2}CO→D_{2}+CO.
 Publication:

Journal of Chemical Physics
 Pub Date:
 October 1990
 DOI:
 10.1063/1.459636
 Bibcode:
 1990JChPh..93.5657M
 Keywords:

 Decomposition;
 Formaldehyde;
 Hamiltonian Functions;
 Quantum Chemistry;
 Statistical Distributions;
 Deuterium;
 Distribution Functions;
 Electron Transitions;
 Ground State;
 Perturbation Theory;
 Atomic and Molecular Physics