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Solvation thermodynamics of neutral and charged solutes using the solvation‐layer interface condition continuum dielectric model
Author(s) -
Mehdizadeh Rahimi Ali,
Molavi Tabrizi Amirhossein,
Goossens Spencer,
Knepley Matthew G.,
Bardhan Jaydeep P.
Publication year - 2019
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25771
Subject(s) - solvation , chemistry , implicit solvation , electrostatics , water model , dielectric , dipole , thermodynamics , molecular dynamics , solvophobic , chemical physics , solvation shell , solvent , computational chemistry , physics , organic chemistry , quantum mechanics
We demonstrate that the solvation‐layer interface condition (SLIC) continuum dielectric model for molecular electrostatics, combined with a simple solvent‐accessible‐surface‐area (SASA)‐proportional model for nonpolar solvent effects, accurately predicts solvation entropies of neutral and charged small molecules. The SLIC/SASA model has only seven fitting parameters in total and achieves this accuracy using a training set with only 20 compounds. Despite this simplicity, solvation free energies and entropies are nearly as accurate as those predicted by the more sophisticated Langevin dipoles solvation model. Surprisingly, the model automatically reproduces the negligible contribution of electrostatics to the solvation of hydrophobic compounds. Opportunities for improvement include nonpolar solvation, anion solvation entropies, and heat capacities. More molecular realism may be needed for these quantities. To enable a future, explicit‐solvent‐based assessment of the SLIC/SASA implicit‐solvent model, we predict solvation entropies for the Mobley test set, which are available as Supporting Information.