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

Garcia-Ratés, M., & Neese, F. (2020). Effect of the Solute Cavity on the Solvation Energy and its Derivatives within the Framework of the Gaussian Charge Scheme. Journal of Computational Chemistry, 41(9), 922-939. doi:10.1002/jcc.26139.

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 Creators:
Garcia-Ratés, Miquel1, Author              
Neese, Frank2, Author              
Affiliations:
1Research Group Pantazis, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541711              
2Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              

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Free keywords: C-PCM; density functional theory; implicit solvation
 Abstract: 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.

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Language(s): eng - English
 Dates: 2019-11-082019-12-152019-12-302020-04-05
 Publication Status: Published in print
 Pages: 18
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/jcc.26139
 Degree: -

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Title: Journal of Computational Chemistry
  Abbreviation : J. Comput. Chem.
Source Genre: Journal
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Publ. Info: New York : Wiley
Pages: - Volume / Issue: 41 (9) Sequence Number: - Start / End Page: 922 - 939 Identifier: ISSN: 0192-8651
CoNE: https://pure.mpg.de/cone/journals/resource/954925489848