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Published July 7, 2016 | Accepted Version + Supplemental Material
Journal Article Open

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


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.

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.

Attached Files

Accepted Version - acs_2Ejpcb_2E6b03295.pdf

Supplemental Material - jp6b03295_si_001.pdf


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