Self consistent field theory of solvent effects representation by continuum models: Introduction of desolvation contribution

Abstract

We examine the representation of solvent effects by continuum models in the frame of the Reaction Field Theory. Particular attention is devoted to the problem raised by the adaptation of the current methods of Quantum Chemistry in the Self Consistent Field approximation especially at a semiempirical level.A critical examination of the literature in the field shows that, for the main part, the proposed methods suffer from theoretical internal incoherence.As an illustration of this study, we propose an extension of the generalized Born formula which is able to account for the desolvation effects produced by the specific neighborhood of each center of the solvated species.

Solvatochromic Effect in a Benzimidazole-Based Betaine: Determination of the Dipole Moments and Second-Order Hyperpolarizability

“…The method enables calculation of parameters of ground and excited state of isolated molecules, molecular complexes and transition metal compounds within a unifled parametrization scheme, in a reasonable agreement with relevant experimental results. In additional calculations we also included the solvent effect via the virtual charge method (VCM) of Constanciel and Tapia [20][21][22]. These results will be reported elswhere [23].…”

Implicit solvation based on generalized Born theory in different dielectric environments

“…An approximation to the reaction field energy can also be obtained with the generalized Born ͑GB͒ formalism in a pairwise sum over interacting charges 12,13 …”

Quantum mechanical calculation of thermodynamic functions of solvation of ammonium ions in water

“…It is expressed as a function of the net charges QA(P) associated with the atomic A-center of the solute, the two electron Coulomb integrals y,,, representing the solute-solvent interaction, and the bulk dielectric constant of the solvent ED. Although some confusion concerning the physical meaning of this energy has been made in the literature (19,20), it has been emphasized recently (21,22) that the quantity AEs represents the free energy variation of the solute-solvent system, maintained at a given temperature, when the polarized solute is transferred from the gas phase to the solvent.…”

“…As was proposed recently (22), the total free energy of the solute-solvent system is obtained by adding to the total energy of the isolated solute, the electrostatic solvation energy A G S (~L , EO, P ) which corresponds to the free energy variation of the solute-solvent system, when the polarized solute is inserted isothermically into the solvent. This solvation term may be where E , 7 -z (~L , E D , P ) (eq.…”