Modelling unimolecular reactions

Abstract

Reaction rates for unimolecular isomerization reactions are estimated from a model where minimal information is provided from ab initio electronic-structure calculations. The dynamic problem is formulated as a two-dimensional quantum mechanical motion in a subspace of the nuclear conformations defined by the geometry of the reactant, the transition state, and the product. Energy data at these geometries, preferably also Hessian information, is utilized to generate a surface.