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
SolvationImplicit solvationBasis setChemistryPolarizabilityMoleculeSolvation shellIonComputationSeries (stratigraphy)Computational chemistryBasis (linear algebra)Polarizable continuum modelAtomic physicsThermodynamicsStatistical physicsPhysicsDensity functional theoryMathematicsAlgorithmGeometry
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Publication Info
- Year
- 1997
- Type
- article
- Volume
- 107
- Issue
- 8
- Pages
- 3210-3221
- Citations
- 2374
- Access
- Closed
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Cite This
Vincenzo Barone,
Maurizio Cossi,
Jacopo Tomasi
(1997).
A new definition of cavities for the computation of solvation free energies by the polarizable continuum model.
The Journal of Chemical Physics
, 107
(8)
, 3210-3221.
https://doi.org/10.1063/1.474671
Identifiers
- DOI
- 10.1063/1.474671