title: Quantum and dynamical effects of proton donor-acceptor vibrational motion in nonadiabatic proton-coupled electron transfer reactions.
abstract: This paper presents a general theoretical formulation for proton-coupled electron transfer (PCET) reactions. The solute is represented by a multistate valence bond model, and the active electrons and transferring proton(s) are treated quantum mechanically. This formulation enables the classical or quantum mechanical treatment of the proton donor-acceptor vibrational mode, as well as the dynamical treatment of the proton donor-acceptor mode and the solvent. Nonadiabatic rate expressions are presented for PCET reactions in a number of well-defined limits for both dielectric continuum and molecular representations of the environment. The dynamical rate expressions account for correlations between the fluctuations of the proton donor-acceptor distance and the nonadiabatic PCET coupling. The quantities in the rate expressions can be calculated with a dielectric continuum model or a molecular dynamics simulation of the full system. The significance of the quantum and dynamical effects of the proton donor-acceptor mode is illustrated with applications to model PCET systems.
authors.affiliation: Department of Chemistry, Pennsylvania State University, University Park, PA 16802, USA.
authors.forename: Alexander
authors.initials: A
authors.lastname: Soudackov
authors.forename: Elizabeth
authors.initials: E
authors.lastname: Hatcher
authors.forename: Sharon
authors.initials: S
authors.lastname: Hammes-Schiffer
mesh_terms: D003198:Computer Simulation; D004579:Electron Transport; D004583:Electrons; D004735:Energy Transfer; D008956:Models, Chemical; D008958:Models, Molecular; D009038:Motion; D011522:Protons; D011789:Quantum Theory; D014732:Vibration
chemical_list: D011522:Protons