Molecular properties in solution described with a continuum solvation model (original) (raw)
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The extended polarizable continuum model for calculation of solvent effects
Journal of Molecular Structure: THEOCHEM, 1988
An extended version of the polarixable continuum model of solvation is presented. Principles of the particular models for electrostatic, dispersion, repulsion, and cavitation terms evaluation are shown and the recent state in methodology is described. Modifications suitable for large biomolecules, fields of application and possible further development are discussed. An illustrative example showing the significance of individual solvation Gibbs free energy contributions is given.
The Journal of Chemical Physics, 2003
The hybrid molecular-continuum model for polar solvation considered in this paper combines the dielectric continuum approximation for treating fast electronic ͑inertialess͒ polarization effects and a molecular dynamics ͑MD͒ simulation for the slow ͑inertial͒ polarization component, including orientational and translational solvent modes. The inertial polarization is generated by average charge distributions of solvent particles, composed of permanent and induced ͑electronic͒ components. MD simulations are performed in a manner consistent with the choice of solvent and solute charges such that all electrostatic interactions are scaled by the factor 1/ ϱ , where ϱ is the optical dielectric permittivity. This approach yields an ensemble of equilibrium solvent configurations adjusted to the electric field created by a charged or strongly polar solute. The electrostatic solvent response field is found as the solution of the Poisson equation including both solute and explicit solvent charges, with accurate account of electrostatic boundary conditions at the surfaces separating spatial regions with different dielectric permittivities. Both equilibrium and nonequilibrium solvation effects can be studied by means of this model, and their inertial and inertialess contributions are naturally separated. The methodology for computation of charge transfer reorganization energies is developed and applied to a model two-site dipolar system in the SPC water solvent. Three types of charge transfer reactions are considered. The standard linear-response approach yields high accuracy for each particular reaction, but proves to be significantly in error when reorganization energies of different reactions were compared. This result has a purely molecular origin and is absent within a conventional continuum solvent model.
Chemical Physics, 2010
The theory and an implementation of the solvent contribution to the cubic response function for the polarizable continuum model for multiconfigurational self-consistent field wave functions is presented. The excited-state polarizability of benzene, para-nitroaniline, and nitrobenzene has been obtained from the double residue of the cubic response function calculated in the presence of an acetonitrile and dioxane solvent. The calculated excited-state polarizabilities are compared to results obtained from the linear response function of the explicitly optimized excited states.
Journal of Computational Chemistry, 1995
A new formulation (CLS-PCM) for the calculation of the apparent surface charges in the framework of the ab initio polarizable continuum model of the solvent (PCM) is introduced. Its performance is compared with that of the original iterative version (ITER-PCM) of the method as well as with a matricial alternative formulation (matrix-BEM-PCM) of the same problem. Both CLS-PCM and matrix-BEM-PCM have shown to be computationally more efficient than ITER-PCM without presenting any problems associated with the convergence of the process. Although for small and medium-size solutes the use of matrix-BEM-PCM is recommended, for neutral solutes of larger size the use of CLS2 becomes computationally more convenient. Finally, for very large-size systems, compromise between matrix storage requirements, time of calculation, and exactness of the results may make preferable the use of the more approximate CLSl formalism, possibly in conjunction with semiempirical or semiclassical descriptions of the solute.