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Issue 16, 2012
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A modified two-sphere model for solvent reorganization energy in electron transfer

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Abstract

In this work, the solvent reorganization energy is formulated within the framework of classical thermodynamics, by adding some external charges to construct a constrained equilibrium state. The derivation clearly shows that the reorganization energy is exactly the polarization cost for the inertial part of the polarization. We perform our derivation just within the framework of the first law of thermodynamics, and the final form of the reorganization energy is completely the same as that we gave in our recent work by defining a nonequilibrium solvation free energy. With the two-sphere model approximation, our solvent reorganization energy is derived as Image ID:c2cp23759h-t1.gif. This amends Marcus' model by a factor of (ε−1opε−1s)/(1 − ε−1s), which is coupled with the solvent polarity. Making use of the modified expression of solvent reorganization energy, two recently reported electron transfer processes are investigated in representative solvents. The results show that our formula can well reproduce the experimental observations.

Graphical abstract: A modified two-sphere model for solvent reorganization energy in electron transfer

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Article information


Submitted
28 Nov 2011
Accepted
17 Feb 2012
First published
17 Feb 2012

Phys. Chem. Chem. Phys., 2012,14, 5538-5544
Article type
Paper

A modified two-sphere model for solvent reorganization energy in electron transfer

H. Wu, H. Ren, Q. Zhu and X. Li, Phys. Chem. Chem. Phys., 2012, 14, 5538
DOI: 10.1039/C2CP23759H

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