Derivation of instanton rate theory from first principles

Abstract

Instanton rate theory is used to study tunneling events in a wide range of systems including low-temperature chemical reactions. Despite many successful applications, the method has never been obtained from first principles, relying instead on the "ImF" premise. In this paper, the same expression for the rate of barrier penetration at finite temperature is rederived from quantum scattering theory [W. H. Miller, S. D. Schwartz, and J. W. Tromp, J. Chem. Phys. 79, 4889 (1983)] using a semiclassical Green's function formalism. This justifies the instanton approach and provides a route to deriving the rate of other processes.

7 pages, 2 figures

References in corpus (3)

• Derivation of instanton rate theory from first principles
• Semiclassical Green's functions and an instanton formulation of electron-transfer rates in the nonadiabatic limit
• Ring-polymer instanton theory of electron transfer in the nonadiabatic limit

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