A THEORY FOR THE ACTIVATED BARRIER CROSSING RATE-CONSTANT IN SYSTEMS INFLUENCED BY SPACE AND TIME-DEPENDENT FRICTION

Citation
Gr. Haynes et al., A THEORY FOR THE ACTIVATED BARRIER CROSSING RATE-CONSTANT IN SYSTEMS INFLUENCED BY SPACE AND TIME-DEPENDENT FRICTION, The Journal of chemical physics, 101(9), 1994, pp. 7811-7822
Citations number
125
Categorie Soggetti
Physics, Atomic, Molecular & Chemical
ISSN journal
00219606
Volume
101
Issue
9
Year of publication
1994
Pages
7811 - 7822
Database
ISI
SICI code
0021-9606(1994)101:9<7811:ATFTAB>2.0.ZU;2-U
Abstract
A general theory is presented for the thermally activated rate constan t in systems influenced by spatially dependent and. time correlated fr iction. The theory is valid at all damping strengths and goes uniforml y from the energy diffusion limit to the spatial diffusion limit. Resu lts of the theory for a model system with an exponentially time correl ated and spatially dependent friction kernel are compared with results from a numerically exact solution of the equivalent generalized Lange vin equation. Predictions of the theory are found to be in excellent a greement with the numerical simulation results. The phenomenon of memo ry suppression of the rate is observed for long time scale frictions a nd its modification due to the spatial dependence of the friction is d iscussed. The effects of spatially dependent friction can be understoo d through a quantity called the ''average spatial modification'' of th e coupling between the reaction coordinate and the environment.