A new method to locate saddle points for reactions in solution by using the free-energy gradient method and the mean field approximation

I Fdez Galván; M E Martín; M A Aguilar

doi:10.1002/jcc.20048

A new method to locate saddle points for reactions in solution by using the free-energy gradient method and the mean field approximation

J Comput Chem. 2004 Jul 30;25(10):1227-33. doi: 10.1002/jcc.20048.

Authors

I Fdez Galván¹, M E Martín, M A Aguilar

Affiliation

¹ Dpto Química Física, Universidad de Extremadura, Avda. de Elvas s/n, 06071, Badajoz, Spain.

PMID: 15139035
DOI: 10.1002/jcc.20048

Abstract

A new method for calculating saddle points of reactions in solution is presented. The main characteristics of the method are: (1) the solute-solvent system is described by the averaged solvent electrostatic potential/molecular dynamics method (ASEP/MD). This is a quantum mechanics/molecular mechanics method (QM/MM) that makes use of the mean field approximation (MFA) and that permits one to simultaneously optimize the electronic structure and geometry of the solute molecule and the solvent structure around it. (2) The transition state is located by the joint use of the free-energy gradient method and the mean field approximation. An application to the study of the Menshutkin reaction between NH(3) and CH(3)Cl in aqueous solution is discussed. The accuracy and usefulness of the proposed method is checked through comparison with other methods.