New Model for Calculation of Solvation Free Energies: Correction of Self-Consistent Reaction Field Continuum Dielectric Theory for Short-Range Hydrogen-Bonding Effects

Autor:	Bryan Marten, Kyungsun Kim, Christian Cortis, Richard A. Friesner, Robert B. Murphy, Murco N. Ringnalda, Doree Sitkoff, Barry Honig
Rok vydání:	1996
Předmět:	Aqueous solution Hydrogen bond Chemistry General Engineering Solvation Ab initio Perturbation (astronomy) Dielectric Molecular physics Molecular mechanics Molecule Physics::Chemical Physics Physical and Theoretical Chemistry Atomic physics
Zdroj:	The Journal of Physical Chemistry. 100:11775-11788
ISSN:	1541-5740 0022-3654
DOI:	10.1021/jp953087x
Popis:	We present self-consistent reaction field (SCRF) calculations, utilizing correlated ab initio quantum mechanics, of aqueous solvation free energies for a large data base of molecular solutes. We identify a subset of chemical functional groups for which there are systematic deviations in the comparison of theory and experiment; furthermore, for one case which has been extensively investigated, methylated amines, similar deviations appear in explicit solvent free energy perturbation calculations employing several commonly used molecular mechanics potential functions. By carrying out high-level ab initio quantum chemical calculations of hydrogen-bonding energies of the solutes to a water molecule, we arrive at a coherent explanation of the disagreements between theory and experiment, namely, that hydrogen-bonding energies are in some cases poorly correlated with classical electrostatic interaction energies. We show that the deviation in hydrogen-bonding energies of a solute from a reference molecule (for whi...
Databáze:	OpenAIRE
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