NDLI: Analysis of kinetic isotope effects for proton-coupled electron transfer reactions.

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Analysis of kinetic isotope effects for proton-coupled electron transfer reactions.

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Soudackov, Alexander V. Hammes-schiffer, Sharon Edwards, Sarah J.
Description	Author Affiliation: Edwards SJ ( Department of Chemistry, 104 Chemistry Building, Pennsylvania State University, University Park, Pennsylvania 16802, USA.)
Abstract	A series of rate constant expressions for nonadiabatic proton-coupled electron transfer (PCET) reactions are analyzed and compared. The approximations underlying each expression are enumerated, and the regimes of validity for each expression are illustrated by calculations on model systems. In addition, the kinetic isotope effects (KIEs) for a series of model PCET reactions are analyzed to elucidate the fundamental physical principles dictating the magnitude of the KIE and the dependence of the KIE on the physical properties of the system, including temperature, reorganization energy, driving force, equilibrium proton donor-acceptor distance, and effective frequency of the proton donor-acceptor mode. These calculations lead to three physical insights that are directly relevant to experimental data. First, these calculations provide an explanation for a decrease in the KIE as the proton donor-acceptor distance increases, even though typically the KIE will increase with increasing equilibrium proton donor-acceptor distance if all other parameters remain fixed. Often the proton donor-acceptor frequency decreases as the proton donor-acceptor distance increases, and these two effects impact the KIE in opposite directions, so either trend could be observed. Second, these calculations provide an explanation for an increase in the KIE as the temperature increases, even though typically the KIE will decrease with increasing temperature if all other parameters remain fixed. The combination of a rigid hydrogen bond, which corresponds to a high proton donor-acceptor frequency, and low solvent polarity, which corresponds to small solvent reorganization energy, allows the KIE to either increase or decrease with temperature, depending on the other properties of the system. Third, these calculations provide insight into the dependence of the rate constant and KIE on the driving force, which has been studied experimentally for a wide range of PCET systems. The rate constant increases as the driving force becomes more negative because excited vibronic product states associated with low free energy barriers and relatively large vibronic couplings become accessible. The ln[KIE] has a maximum near zero driving force and decreases significantly as the driving force becomes more positive or negative because the contributions from excited vibronic states increase as the reaction becomes more asymmetric, and contributions from excited vibronic states decrease the KIE. These calculations and analyses lead to experimentally testable predictions of trends in the KIEs for PCET systems.
ISSN	10895639
e-ISSN	15205215
Journal	The Journal of Physical Chemistry A
Issue Number	10
Volume Number	113
Language	English
Publisher	American Chemical Society (United States)
Publisher Date	2009-03-12
Publisher Place	United States
Access Restriction	Open
Subject Keyword	Deuterium Chemistry Electron Transport Models, Chemical Protons Hydrogen Kinetics Temperature Research Support, N.I.H., Extramural Research Support, U.S. Gov't, Non-P.H.S. Physical chemistry
Content Type	Text
Resource Type	Article
Subject	Medicine Physical and Theoretical Chemistry

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