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Abstract
Linearized microscopic theories of equilibrium solvation can be straightforwardly extended to treat the dynamic situation. A particular example, the solvation of a newly formed ion, is developed within the mean spherical approximation. The MSA exhibits significant deviations from the Born–Marcus formula for nonequilibrium solvation energies. The solvation dynamics proceeds on several time scales. The solvation structure first forms distant from the ion, in harmony with a remark of Onsager and with previous numerical calculations of Calef and Wolynes [J. Chem. Phys. 78, 4145 (1983)].
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