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

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 solve...

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Vydané v:Journal of computational chemistry Ročník 41; číslo 9; s. 922 - 939
Hlavní autori: Garcia‐Ratés, Miquel, Neese, Frank
Médium: Journal Article
Jazyk:English
Vydavateľské údaje: Hoboken, USA John Wiley & Sons, Inc 05.04.2020
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Predmet:
Accuracy
Computational chemistry
Computing costs
Conductors
Continuum modeling
C‐PCM
density functional theory
Energy gradient
Free energy
implicit solvation
Mathematical analysis
Model accuracy
Organic chemistry
Potential energy
Solvation
Solvents
implicit solvation
C-PCM
density functional theory
ISSN:0192-8651, 1096-987X, 1096-987X
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Shrnutí: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. In this article, we study the effect of the solute cavity within the framework of the conductor‐like polarizable continuum model. Our solvation approach combines a treatment of the electrostatic part of the solvation energy (ΔG solv) based on Gaussian charges, together with a nonelectrostatic contribution depending on the solvent‐accessible surface. Our results for the solvation energy of organic solutes in different solvents agree with experimental data with an accuracy lower than 1 kcal/mol.
Bibliografia:Funding information
Deutsche Forschungsgemeinschaft, Grant/Award Numbers: EXC 2033 / Projektnummer 390677874, SPP 1601; Max‐Planck‐Gesellschaft
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ISSN:0192-8651
1096-987X
1096-987X
DOI:10.1002/jcc.26139