Analytic continuation of Wolynes theory into the Marcus inverted regime

Journal article

The Wolynes theory of electronically nonadiabatic reaction rates [P. G. Wolynes, J. Chem. Phys. 87, 6559 (1987)] is based on a saddle point approximation to the time integral of a reactive flux autocorrelation function in the nonadiabatic (golden rule) limit. The dominant saddle point is on the imaginary time axis at tsp=iλspℏtsp=iλspℏ, and provided λsp lies in the range −β/2≤λsp≤β/2−β/2≤λsp≤β/2, it is straightforward to evaluate the rate constant using information obtained from an imaginary ...

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Authors: Lawrence, J; Manolopoulos, D

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: AIP Publishing
• Journal: Journal of Chemical Physics
• Volume: 148
• Issue: 10
• Article number: 102313
• Publication date: 2017-10-30
• Acceptance date: 2017-10-06
• DOI: 10.1063/1.5002894
• EISSN: 1089-7690
• ISSN: 0021-9606
• Keywords: physics.chem-ph