Marcus, R. A. (1984) Nonadiabatic processes involving quantum-like and classical-like coordinates with applications to nonadiabatic electron transfers. Journal of Chemical Physics, 81 (10). pp. 4494-4500. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20120629-141832137
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Nonadiabatic processes may involve both classical‐like and quantum‐like coordinates. A semiclassical analysis is used to treat the contribution of the former to the Franck–Condon factor in the reaction rate expression, thereby avoiding the usual harmonic oscillator approximation. Microcanonical and canonical rate constants are calculated, yielding an expression which includes contributions from both types of coordinates. The results are applied to nonadiabatic electron transfer reactions in solution, and show how ΔG^0 enters the final rate expression, even though ΔE^0 is present in the initial Golden Rule nonadiabatic formula. This result avoids an approximation which has arisen in the nonadiabatic electron transfer literature.
|Additional Information:||© 1984 American Institute of Physics. Received 4 June 1984; accepted 5 July 1984. It is a pleasure to acknowledge support of this research by the National Science Foundation.|
|Subject Keywords:||franck−condon principle; solutions; electron transfer; chemical reaction kinetics; coordinates|
|Classification Code:||PACS: 82.20.Pm|
|Official Citation:||Nonadiabatic processes involving quantum-like and classical-like coordinates with applications to nonadiabatic electron transfers R. A. Marcus, J. Chem. Phys. 81, 4494 (1984), DOI:10.1063/1.447418|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Jason Perez|
|Deposited On:||02 Jul 2012 15:35|
|Last Modified:||26 Dec 2012 15:26|
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