Quantum and dynamical effects of proton donor-acceptor vibrational motion in nonadiabatic proton-coupled electron transfer reactions.
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.
Soudackov
Alexander
A
Department of Chemistry, Pennsylvania State University, University Park, PA 16802, USA.
Hatcher
Elizabeth
E
Hammes-Schiffer
Sharon
S
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
D011522:Protons