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Thermodynamics for nonequilibrium solvation and numerical evaluation of solvent reorganization energy

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Abstract

This work presents a thermodynamic method for treating nonequilibrium solvation. By imposing an extra electric field onto the nonequilibrium solvation system, a virtual constrained equilibrium state is prepared. In this way, the free energy difference between the real nonequilibrium state and the constrained equilibrium one is simply the potential energy of the nonequilibrium polarization in the extra electronic field, according to thermodynamics. Further, new expressions of nonequilibrium solvation energy and solvent reorganization energy have been formulated. Analysis shows that the present formulations will give a value of reorganization energy about one half of the traditional Marcus theory in polar solvents, thus the explanation on why the traditional theory tends to overestimate this quantity has been found out. For the purpose of numerical determination of solvent reorganization energy, we have modified Gamess program on the basis of dielectric polarizable continuum model. Applying the procedure to the well-investigated intramolecular electron transfer in biphenyl-androstane-naphthyl and biphenyl-androstane-phenanthryl systems, the numerical results of solvent reorganization energy have been found to be in good agreement with the experimental fittings.

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Authors and Affiliations

  1. College of Chemical Engineering, Sichuan University, Chengdu, 610065, China

    XiangYuan Li, JingBo Wang, JianYi Ma, KeXiang Fu & FuCheng He

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  1. XiangYuan Li
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Correspondence to XiangYuan Li.

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Supported by the National Natural Science Foundation of China (Grant Nos. 20533070 and 20625311)

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Li, X., Wang, J., Ma, J. et al. Thermodynamics for nonequilibrium solvation and numerical evaluation of solvent reorganization energy. Sci. China Ser. B-Chem. 51, 1246–1256 (2008). https://doi.org/10.1007/s11426-008-0138-9

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  • DOI: https://doi.org/10.1007/s11426-008-0138-9

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