A Caltech Library Service

Molecularly-Based Theory for Electron Transfer Reorganization Energy in Solvent Mixtures

Zhuang, Bilin and Wang, Zhen-Gang (2016) Molecularly-Based Theory for Electron Transfer Reorganization Energy in Solvent Mixtures. Journal of Physical Chemistry B, 120 (26). pp. 6373-6382. ISSN 1520-6106. doi:10.1021/acs.jpcb.6b03295.

[img] PDF - Accepted Version
See Usage Policy.

[img] PDF (Details of the derivation of the constitutive relations and a comparison between the activation energies calculated with the DSCFT and with the MD simulation for the ferrous/ferric exchange reaction in water/methanol mixture) - Supplemental Material
See Usage Policy.


Use this Persistent URL to link to this item:


Using statistical-field techniques, we develop a molecular-based dipolar self-consistent-field theory (DSCFT) for charge solvation in liquid mixtures under equilibrium and nonequilibrium conditions, and apply it to compute the solvent reorganization energy of electron-transfer reactions. In addition to the nonequilibrium orientational polarization, the reorganization energy in liquid mixtures is also determined by the out-of-equilibrium solvent composition around the reacting species due to preferential solvation. Using molecular parameters that are readily available, the DSCFT naturally accounts for the dielectric saturation effect and the spatially varying solvent composition in the vicinity of the reacting species. We identify three general categories of binary solvent mixtures, classified by the relative optical and static dielectric permittivities of the solvent components. Each category of mixture is shown to produce a characteristic local solvent composition profile in the vicinity of the reacting species, which gives rise to the distinctive composition dependence of the reorganization energy that cannot be predicted using the dielectric permittivities of the homogeneous solvent mixtures.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Zhuang, Bilin0000-0003-2934-4264
Wang, Zhen-Gang0000-0002-3361-6114
Additional Information:© 2016 American Chemical Society. Received: March 31, 2016. Revised: May 17, 2016. Publication Date (Web): May 17, 2016. Special Issue: William M. Gelbart Festschrift. We thank Professors Rudolph Marcus, Thomas Miller III, David Tirrell, and Mr. Kevin Shen for helpful discussions. B.Z. gratefully acknowledges the support by an A-STAR fellowship. Acknowledgment is also made to the donors of the American Chemical Society Petroleum Research Fund for partial support of this research. The authors declare no competing financial interest.
Funding AgencyGrant Number
Agency for Science, Technology and Research (A*STAR)UNSPECIFIED
American Chemical Society Petroleum Research FundUNSPECIFIED
Issue or Number:26
Record Number:CaltechAUTHORS:20160524-080318394
Persistent URL:
Official Citation:Molecular-Based Theory for Electron-Transfer Reorganization Energy in Solvent Mixtures Bilin Zhuang and Zhen-Gang Wang The Journal of Physical Chemistry B 2016 120 (26), 6373-6382 DOI: 10.1021/acs.jpcb.6b03295
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:67283
Deposited By: Tony Diaz
Deposited On:24 May 2016 18:43
Last Modified:11 Nov 2021 00:30

Repository Staff Only: item control page