A generalization of Wolynes factor in activated processes

Details A generalization of Wolynes factor in activated processes A generalization of Wolynes factor in activated processes

2004-11-10

arxiv.org/abs/cond-mat/0411268v1

Physics

Condensed Matter

Other Condensed Matter

21 pages

Scientific paper

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.

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