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Multidimensional uniform semiclassical instanton thermal rate theory.
- 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]
- Subjects :
- INSTANTONS
SEMICLASSICAL limits
SYSTEMS theory
TUNNEL design & construction
Subjects
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