A generalization of Wolynes factor in activated processes

TL;DR

This paper proposes a generalized Wolynes factor based on quantum normal mode analysis, extending the validity of quantum rate corrections to deep tunneling regions down to absolute zero.

Contribution

It introduces a new multidimensional transition state rate expression that remains valid in deep tunneling regimes, surpassing previous limitations.

Findings

Validates the generalized Wolynes factor at low temperatures

Provides a multidimensional rate expression applicable to deep tunneling

Extends quantum correction applicability to zero Kelvin

Abstract

Kramers-Grote-Hynes factor is the key nonequilibrium contribution to rate constant of a reaction over and above the transition state theory rate in the spatial limited regime. Wolynes in eighties introduced a quantum correction to the overall rate coefficient. This is responsible for tunneling and quantum enhancement of rate at low temperature. However, its validity is restricted to activated tunneling region or above crossover temperature. Based on a quantum formulation of the normal mode analysis, we suggest a generalization of Wolynes factor and a consequent multidimensional transition state rate expression which are valid in the deep tunneling region down to zero degree Kelvin.