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Multidimensional uniform semiclassical instanton thermal rate theory.

Authors :
Pollak, Eli
Source :
Journal of Chemical Physics; 12/14/2023, Vol. 159 Issue 22, p1-7, 7p
Publication Year :
2023

Abstract

Instanton-based rate theory is a powerful tool that is used to explore tunneling in many-dimensional systems. Yet, it diverges at the so-called "crossover temperature." Using the uniform semiclassical transmission probability of Kemble [Phys. Rev. 48, 549 (1935)], we showed recently that in one dimension, one might derive a uniform semiclassical instanton rate theory, which has no divergence. In this paper, we generalize this uniform theory to many-dimensional systems. The resulting theory uses the same input as in the previous instanton theory, yet does not suffer from the divergence. The application of the uniform theory to dissipative systems is considered and used to revise Wolynes' well-known analytical expression for the rate [P. G. Wolynes, Phys. Rev. Lett. 47, 968 (1981)] so that it does not diverge at the "crossover temperature." [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
00219606
Volume :
159
Issue :
22
Database :
Complementary Index
Journal :
Journal of Chemical Physics
Publication Type :
Academic Journal
Accession number :
174233632
Full Text :
https://doi.org/10.1063/5.0182422