Analysis of the reaction force for a gas phase S(N)2 process: CH3Cl + H2O --> CH3OH + HCl

Abstract

The "reaction force" F(R(c)) is the negative derivative of a system's potential energy V(R(c)) along the intrinsic reaction coordinate of a process. If V(R(c)) goes through a maximum, as is commonly the case, then F(R(c)) has a characteristic profile: a negative minimum followed by zero at the transition state and then a positive maximum. These features reflect four phases of the reaction: an initial one of reactant preparation, followed by two of transition to products, and then relaxation of the latter. In this study, we have analyzed, in these terms, a gas-phase S(N)2 substitution, selected to be CH3Cl + H2O --> CH3OH + HCl. We examine, at the B3LYP/6-31G level, the geometries, energetics, and molecular surface electrostatic potentials, local ionization energies, and internal charge separation.