Numerical solution of solvent reorganization energy and its application in electron transfer reaction

Ting Jun Bi, Mei Jun Ming, Hai Sheng Ren, Jian Yi Ma, Xiang Yuan Li

Research output: Contribution to journalArticlepeer-review

Abstract

According to our recent studies on the nonequilibrium solvation, the solvent reorganization energy λs is found to be the cost of maintaining the residual polarization, which equilibrates with the constraining extra electric field. In this work, a matrix form of λs has been formulated based our new analytical expression of the solvent reorganization energy. By means of the integral equation formulation-polarizable continuum model (IEF-PCM), a new numerical algorithm for λs has been implemented as a subroutine coupled with the Q-Chem package. Then, we have performed a comparison of numerical results with analytical solution obtained by two-sphere model for λs in self-exchange electron transfer (ET) reaction of He-He+ system. The numerical results and analytical solution coincide as the distance between the donor and the acceptor. In order to compare with our pervious numerical algorithm with dielectric polarizable continuum model, self-exchange ET reactions between tetracyanoethylene, tetrathiafulvalene, and their corresponding ionic radicals in acetonitrile have been studied. Overall, the solvent reorganization energy calculated by IEF-PCM is more reasonable since IEF-PCM gives a better self-energy of surface element.

Original languageEnglish (US)
JournalTheoretical Chemistry Accounts
Volume133
Issue number10
DOIs
StateAccepted/In press - Aug 27 2014

Keywords

  • Constrained density functional theory
  • Constrained equilibrium
  • Electron transfer
  • Numerical solution
  • Two-sphere model

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