A new definition of cavities for the computation of solvation free energies by the polarizable continuum model
- 22 August 1997
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 107 (8) , 3210-3221
- https://doi.org/10.1063/1.474671
Abstract
A set of rules for determining the atomic radii of spheres used to build the molecular cavities in continuum solvation models are presented. The procedure is applied to compute the hydration free energy for molecules containing H, C, N, O, F, P, S, Cl, Br, and I at a computational level (Hartree–Fock with a medium size basis set) allowing the study of relatively large systems. The optimized radii reduce the mean error with respect to the experimental solvation energies below 0.20 kcal/mol for a set of 43 neutral solutes and around 1 kcal/mol for 27 ions. Moreover the correct trends are observed for the solvation energies of homolog series, like the series ammonia–trimethylamine, that are not correctly reproduced by usual solvation models.Keywords
This publication has 29 references indexed in Scilit:
- New Model for Calculation of Solvation Free Energies: Correction of Self-Consistent Reaction Field Continuum Dielectric Theory for Short-Range Hydrogen-Bonding EffectsThe Journal of Physical Chemistry, 1996
- Gas-Phase Non-Identity SN2 Reactions of Halide Anions with Methyl Halides: A High-Level Computational StudyJournal of the American Chemical Society, 1996
- Analytical expressions of the free energy derivatives for molecules in solution. Application to the geometry optimizationInternational Journal of Quantum Chemistry, 1995
- Molecular Interactions in Solution: An Overview of Methods Based on Continuous Distributions of the SolventChemical Reviews, 1994
- Quantum Chemical Conformational Analysis of 1,2-Ethanediol: Correlation and Solvation Effects on the Tendency To Form Internal Hydrogen Bonds in the Gas Phase and in Aqueous SolutionJournal of the American Chemical Society, 1994
- Optimization of solute cavities and van der Waals parameters in ab initio MST‐SCRF calculations of neutral moleculesJournal of Computational Chemistry, 1994
- Dispersion and repulsion contributions to the solvation energy: Refinements to a simple computational model in the continuum approximationJournal of Computational Chemistry, 1991
- Evaluation of the dispersion contribution to the solvation energy. A simple computational model in the continuum approximationJournal of Computational Chemistry, 1989
- Ionization potentials and electron affinities in aqueous solutionJournal of the American Chemical Society, 1986
- On the conformational varieties of acetylcholine in the crystals of its halidesActa Crystallographica Section B: Structural Science, Crystal Engineering and Materials, 1978