SOLVENT SLOW-MODE INFLUENCE ON CHEMICAL-REACTION DYNAMICS - A MULTIDIMENSIONAL KRAMERS-THEORY TREATMENT

A theory treating the influence of the heat-bath slow mode on condensed-phase chemical-reaction dynamics is suggested. We have shown that this mode becomes a reaction coordinate in such situations when friction along this mode becomes extremely high and relaxation enormously slow. For calculation of the rate constant in such situations, we have worked out a generalization of the multidimensional Kramers theory for the case of drastically anisotropic friction . Based on this generalization a new expression for the rate constant is derived. In this expression both the activation energy and the preexponent factor are different from the corresponding quantities in the conventional expression which is inapplicable in this case. © 1990.