Derivation of instanton rate theory from first principles

Richardson, Jeremy O.

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 “Im F” 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.

Citation

Richardson, J. O. (2016). Derivation of instanton rate theory from first principles. The Journal of Chemical Physics, 144(11), Article 114106. https://doi.org/10.1063/1.4943866

• Journal Article Type: Article
• Acceptance Date: Mar 1, 2016
• Online Publication Date: Mar 17, 2016
• Publication Date: Mar 21, 2016
• Deposit Date: Feb 7, 2016
• Publicly Available Date: Mar 23, 2016
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 144
• Issue: 11
• Article Number: 114106
• DOI: https://doi.org/10.1063/1.4943866
• Public URL: https://durham-repository.worktribe.com/output/1412965
• Related Public URLs: http://arxiv.org/abs/1508.05195