AN ANALYTIC HINDERED ROTOR MODEL FOR CALCULATING MICROCANONICAL VARIATIONAL UNIMOLECULAR RATE CONSTANTS FROM REACTION-PATH PROPERTIES

A model is proposed for performing microcanonical variational transition state theory calculations which incorporates ideas from vibrator and flexible variational transition state models. Vibrational frequencies, moments of inertia, and potential energy for the variational transition state are found by reaction path following as for the vibrator model. However, the transitional modes are treated as hindered rotors using an analytic potential and an analytic density of states, which are fit to barriers for hindered rotation determined from reaction path following. The model proposed here differs from the flexible transition state model in that the density of states for the transitional modes is analytic and transitional modes and external rotational angular momenta are uncoupled. For the H + CH3 half arrow right over half left CH4 system, rate constants calculated with this new model are only 6 - 23% smaller on average from those of the flexible transition state model for values of total angular momentum which correspond to average rotational temperatures of 0 - 2000 K. Harmonic frequencies calculated for the transitional modes from the hindered rotor Hamiltonian are in good agreement with the exact values found by a reaction path analysis. (C) 1994 John Wiley & Sons, Inc.