Mean field ring polymer molecular dynamics for electronically nonadiabatic reaction rates. (14th October 2016)

• Record Type: Journal Article
• Authors: Duke, Jessica Ryan; Ananth, Nandini
• Is Part Of: Faraday discussions. Volume 195(2016)
• Page Start: 253
• Page End: 268
• Publication Date: 2016-10-14
• Subjects: Chemistry -- Periodicals; Metallurgy -- Periodicals; Electrochemistry -- Periodicals; 540
• DOI: 10.1039/c6fd00123h
• Languages: English
• ISSNs: 1359-6640

Abstract

Abstract : We present a mean field ring polymer molecular dynamics method to calculate the rate of electron transfer (ET) in multi-state, multi-electron condensed-phase processes. Our approach involves calculating a transition state theory (TST) estimate to the rate using an exact path integral in discrete electronic states and continuous Cartesian nuclear coordinates. A dynamic recrossing correction to the TST rate is then obtained from real-time dynamics simulations using mean field ring polymer molecular dynamics. We employ two different reaction coordinates in our simulations and show that, despite the use of mean field dynamics, the use of an accurate dividing surface to compute TST rates allows us to achieve remarkable agreement with Fermi's golden rule rates for nonadiabatic ET in the normal regime of Marcus theory. Further, we show that using a reaction coordinate based on electronic state populations allows us to capture the turnover in rates for ET in the Marcus inverted regime.