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Equilibrium and nonequilibrium solvation and solute electronic structure
Author(s) -
Kim Hyung J.,
Hynes James T.
Publication year - 1990
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560382480
Subject(s) - solvation , non equilibrium thermodynamics , chemistry , polarizability , implicit solvation , chemical physics , elementary charge , electronic structure , solvent , polarization (electrochemistry) , solvent effects , polar , hamiltonian (control theory) , ionic bonding , thermodynamics , wave function , computational chemistry , electron , atomic physics , ion , physics , molecule , quantum mechanics , organic chemistry , mathematical optimization , mathematics
Abstract When a molecular solute is immersed in a polar and polarizable solvent, the electronic wave function of the solute system is altered compared to its vacuum value; the solute electronic structure is thus solvent‐dependent. Further, the wave function will be altered depending upon whether the polarization of the solvent is or is not in equilibrium with the solute charge distribution. More precisely, while the solvent electronic polarization should be in equilibrium with the solute electronic wave function, the much more sluggish solvent orientational polarization need not be. We call this last situation “non‐equilibrium solvation.” We outline a nonlinear Schrödinger equation approach to these issues. The nonlinearity arises from the self‐consistent aspect that the solute electronic Hamiltonian depends on the solvent electronic polarization which is induced by the solute charge distribution. We illustrate the predictions of the theory for electron transfer reactions, ionic dissociations, and solvation dynamics in polar solvents. Special features of interest include activation barriers that differ markedly from standard predictions, and novel solvent dynamical features.