Journal of Chemical Physics, Vol.110, No.1, 80-87, 1999
A test of quantum transition state theory for a system with two degrees of freedom
A recently formulated quantum transition state theory is applied to scattering over an Eckart barrier coupled bilinearly to a harmonic mode. Results are compared with the numerically exact and the centroid density method computations of McRae ct al. [J. Chem. Phys. 97, 7392 (1992)]. We find that quantum transition state theory is of comparable accuracy to the centroid approximation for all parameter ranges studied.
Keywords:ACTIVATED RATE-PROCESSES;RATE CONSTANTS;NONSEPARABLE SYSTEMS;KRAMERS;MODEL;FORMULATION;WATER