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Extension of solution‐reaction‐surface description to examination of nonequilibrium solvation effect for microsolvated reaction
Author(s) -
Okuno Yoshishige
Publication year - 2000
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/(sici)1097-461x(2000)77:4<791::aid-qua11>3.0.co;2-f
Subject(s) - solvation , chemistry , non equilibrium thermodynamics , reaction rate constant , space (punctuation) , reaction coordinate , thermodynamics , solvent , solvation shell , reaction rate , implicit solvation , limit (mathematics) , solvent effects , computational chemistry , chemical physics , physics , quantum mechanics , kinetics , catalysis , organic chemistry , linguistics , philosophy , mathematical analysis , mathematics
A microscopic method to examine a nonequilibrium solvation effect is reported. The solution reaction is simplified as a barrier‐crossing reaction within a solution reaction surface that corresponds to a two‐dimensional space determined by solute and solvent reactive coordinates. For this simplification, the motions within the space spanned by nonreactive coordinates are frozen. We derive three rate constant expressions: (1) in the nonadiabatic solvation limit, (2) in the equilibrium solvation limit, and (3) of the transition‐state theory. This method was applied to the examination of the contact‐ion‐pair formation of t ‐BuCl in four waters. We found that the nonadiabatic solvation picture overestimates the nonequilibrium solvation effect. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 77: 791–796, 2000