Effect of the Solute Cavity on the Solvation Energy and its Derivatives within the Framework of the Gaussian Charge Scheme.

C-PCM density functional theory implicit solvation

Journal

Journal of computational chemistry
ISSN: 1096-987X
Titre abrégé: J Comput Chem
Pays: United States
ID NLM: 9878362

Informations de publication

Date de publication:
05 Apr 2020
Historique:
received: 08 11 2019
revised: 13 12 2019
accepted: 15 12 2019
pubmed: 1 1 2020
medline: 1 1 2020
entrez: 1 1 2020
Statut: ppublish

Résumé

The treatment of the solvation charges using Gaussian functions in the polarizable continuum model results in a smooth potential energy surface. These charges are placed on top of the surface of the solute cavity. In this article, we study the effect of the solute cavity (van der Waals-type or solvent-excluded surface-type) using the Gaussian charge scheme within the framework of the conductor-like polarizable continuum model on (a) the accuracy and computational cost of the self-consistent field (SCF) energy and its gradient and on (b) the calculation of free energies of solvation. For that purpose, we have considered a large set of systems ranging from few atoms to more than 200 atoms in different solvents. Our results at the DFT level using the B3LYP functional and the def2-TZVP basis set show that the choice of the solute cavity does neither affect the accuracy nor the cost of calculations for small systems (< 100 atoms). For larger systems, the use of a vdW-type cavity is recommended, as it prevents small oscillations in the gradient (present when using a SES-type cavity), which affect the convergence of the SCF energy gradient. Regarding the free energies of solvation, we consider a solvent-dependent probe sphere to construct the solvent-accessible surface area required to calculate the nonelectrostatic contribution to the free energy of solvation. For this part, our results for a large set of organic molecules in different solvents agree with available experimental data with an accuracy lower than 1 kcal/mol for both polar and nonpolar solvents.

Identifiants

pubmed: 31889331
doi: 10.1002/jcc.26139
doi:

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Pagination

922-939

Subventions

Organisme : Deutsche Forschungsgemeinschaft
ID : EXC 2033 / Projektnummer 390677874
Organisme : Deutsche Forschungsgemeinschaft
ID : SPP 1601
Organisme : Max-Planck-Gesellschaft

Informations de copyright

© 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc.

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Auteurs

Miquel Garcia-Ratés (M)

Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr, Germany.

Frank Neese (F)

Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr, Germany.

Classifications MeSH