TY - JOUR
T1 - Quantum and dynamical effects of proton donor-acceptor vibrational motion in nonadiabatic proton-coupled electron transfer reactions
AU - Soudackov, Alexander
AU - Hatcher, Elizabeth
AU - Hammes-Schiffer, Sharon
PY - 2005
Y1 - 2005
N2 - 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.
AB - 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.
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U2 - 10.1063/1.1814635
DO - 10.1063/1.1814635
M3 - Article
C2 - 15638672
AN - SCOPUS:22944452805
SN - 0021-9606
VL - 122
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 1
M1 - 014505
ER -