title: Mixed Quantum-Classical Liouville Approach for Calculating Proton-Coupled Electron-Transfer Rate Constants.
abstract: In this work, we derive a general mixed quantum-classical formula for calculating thermal proton-coupled electron-transfer (PCET) rate constants, starting from the time integral of the quantum flux-flux correlation function. This formula allows for the direct simulation of PCET reaction dynamics via the mixed quantum-classical Liouville approach. Owing to the general nature of the derivation, this formula does not rely on any prior mechanistic assumptions and can be applied across a wide range of electronic and protonic coupling regimes. To test the validity of this formula, we applied it to a reduced model of a condensed-phase PCET reaction. Good agreement with the numerically exact rate constant is obtained, demonstrating the accuracy of our formalism. We believe that this approach constitutes a solid foundation for future investigations of the rates and mechanisms of a wide range of PCET reactions.
authors.affiliation: Department of Chemistry, University of Alberta , Edmonton, Alberta T6G 2G2, Canada.
authors.forename: Farnaz
authors.initials: F
authors.lastname: Shakib
authors.affiliation: Department of Chemistry, University of Alberta , Edmonton, Alberta T6G 2G2, Canada.
authors.forename: Gabriel
authors.initials: G
authors.lastname: Hanna