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A molecularly based theory for electron transfer reorganization energy

Zhuang, Bilin and Wang, Zhen-Gang (2015) A molecularly based theory for electron transfer reorganization energy. Journal of Chemical Physics, 143 (22). Art. No. 224502. ISSN 0021-9606. doi:10.1063/1.4936586.

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Using field-theoretic techniques, we develop a molecularly based dipolar self-consistent-field theory (DSCFT) for charge solvation in pure solvents under equilibrium and nonequilibrium conditions and apply it to the reorganization energy of electron transferreactions. The DSCFT uses a set of molecular parameters, such as the solvent molecule’s permanent dipole moment and polarizability, thus avoiding approximations that are inherent in treating the solvent as a linear dielectric medium. A simple, analytical expression for the free energy is obtained in terms of the equilibrium and nonequilibrium electrostatic potential profiles and electric susceptibilities, which are obtained by solving a set of self-consistent equations. With no adjustable parameters, the DSCFT predicts activation energies and reorganization energies in good agreement with previous experiments and calculations for the electron transfer between metallic ions. Because the DSCFT is able to describe the properties of the solvent in the immediate vicinity of the charges, it is unnecessary to distinguish between the inner-sphere and outer-sphere solvent molecules in the calculation of the reorganization energy as in previous work. Furthermore, examining the nonequilibrium free energy surfaces of electron transfer, we find that the nonequilibrium free energy is well approximated by a double parabola for self-exchange reactions, but the curvature of the nonequilibrium free energy surface depends on the charges of the electron-transferring species, contrary to the prediction by the linear dielectrictheory.

Item Type:Article
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URLURL TypeDescription
Zhuang, Bilin0000-0003-2934-4264
Wang, Zhen-Gang0000-0002-3361-6114
Additional Information:© 2015 AIP Publishing LLC. Received 27 May 2015; accepted 16 November 2015; published online 8 December 2015. We gratefully acknowledge helpful discussions with Professor Rudolph A. Marcus and Professor Thomas F. Miller III. B.Z. acknowledges the A-STAR fellowship for the financial support.
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Agency for Science, Technology and Research (A*STAR)UNSPECIFIED
Issue or Number:22
Record Number:CaltechAUTHORS:20151221-130932462
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Official Citation:A molecularly based theory for electron transfer reorganization energy Zhuang, Bilin and Wang, Zhen-Gang, The Journal of Chemical Physics, 143, 224502 (2015), DOI:
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:63105
Deposited By: Ruth Sustaita
Deposited On:22 Dec 2015 19:23
Last Modified:10 Nov 2021 23:11

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