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The interface of electronic structure and dynamics for reactions in solution
Author(s) -
Chuang YaoYuan,
Cramer Christopher J.,
Truhlar Donald G.
Publication year - 1998
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(1998)70:4/5<887::aid-qua34>3.0.co;2-w
Subject(s) - solvation , chemistry , aqueous solution , separable space , quantum tunnelling , implicit solvation , path (computing) , reaction dynamics , computational chemistry , thermodynamics , statistical physics , chemical physics , quantum mechanics , physics , molecule , mathematics , organic chemistry , mathematical analysis , computer science , programming language
We compare two systematic approaches to the calculation of reaction rates in liquid solutions: the separable equilibrium solvation (SES) approximation and the equilibrium solvation path (ESP) approximation. These approaches are tested for two reactions, ClCH 3 +NH 3 →Cl − +H 3 CNH 3 + (R1) and NH 4 + …N′H 3 →NH 3 …N′H 4 + (R2), both in aqueous solution. The first reaction illustrates the importance of variational optimization of the transition state, and the second illustrates the importance of tunneling. Free energies of solvation are calculated by the Solvation Model 5. All calculations are carried out by the new AMSOLRATE program, which is an interface of the AMSOL and POLYRATE programs. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 70: 887–896, 1998