Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions
- PMID: 19366259
- DOI: 10.1021/jp810292n
Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions
Abstract
We present a new continuum solvation model based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent. The model is called SMD, where the "D" stands for "density" to denote that the full solute electron density is used without defining partial atomic charges. "Continuum" denotes that the solvent is not represented explicitly but rather as a dielectric medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where "universal" denotes its applicability to any charged or uncharged solute in any solvent or liquid medium for which a few key descriptors are known (in particular, dielectric constant, refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the solution of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calculation are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent molecules in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality constants called atomic surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aqueous ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and dimethyl sulfoxide, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaqueous organic solvents and water), and 143 transfer free energies for 93 neutral solutes between water and 15 organic solvents. The elements present in the solutes are H, C, N, O, F, Si, P, S, Cl, and Br. The SMD model employs a single set of parameters (intrinsic atomic Coulomb radii and atomic surface tension coefficients) optimized over six electronic structure methods: M05-2X/MIDI!6D, M05-2X/6-31G, M05-2X/6-31+G, M05-2X/cc-pVTZ, B3LYP/6-31G, and HF/6-31G. Although the SMD model has been parametrized using the IEF-PCM protocol for bulk electrostatics, it may also be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calculations in which the solute is represented by its electron density in real space. This includes, for example, the conductor-like screening algorithm. With the 6-31G basis set, the SMD model achieves mean unsigned errors of 0.6-1.0 kcal/mol in the solvation free energies of tested neutrals and mean unsigned errors of 4 kcal/mol on average for ions with either Gaussian03 or GAMESS.
Similar articles
-
Self-Consistent Reaction Field Model for Aqueous and Nonaqueous Solutions Based on Accurate Polarized Partial Charges.J Chem Theory Comput. 2007 Nov;3(6):2011-33. doi: 10.1021/ct7001418. J Chem Theory Comput. 2007. PMID: 26636198
-
Universal Solvation Model Based on the Generalized Born Approximation with Asymmetric Descreening.J Chem Theory Comput. 2009 Sep 8;5(9):2447-64. doi: 10.1021/ct900312z. Epub 2009 Aug 12. J Chem Theory Comput. 2009. PMID: 26616625
-
Charge-dependent cavity radii for an accurate dielectric continuum model of solvation with emphasis on ions: aqueous solutes with oxo, hydroxo, amino, methyl, chloro, bromo, and fluoro functionalities.J Phys Chem A. 2008 Oct 23;112(42):10604-13. doi: 10.1021/jp804092v. Epub 2008 Sep 25. J Phys Chem A. 2008. PMID: 18816107
-
Unraveling water's entropic mysteries: a unified view of nonpolar, polar, and ionic hydration.Acc Chem Res. 2008 Aug;41(8):957-67. doi: 10.1021/ar7001478. Acc Chem Res. 2008. PMID: 18710198 Review.
-
Ionic volumes in solution.Biophys Chem. 2006 Dec 1;124(3):200-7. doi: 10.1016/j.bpc.2006.04.013. Epub 2006 May 3. Biophys Chem. 2006. PMID: 16793195 Review.
Cited by
-
Exploring Border Conditions for Spontaneous Emergence of Chirality in Allylboration of 1,2,3-Triazolic Aldehydes.Int J Mol Sci. 2024 Oct 20;25(20):11273. doi: 10.3390/ijms252011273. Int J Mol Sci. 2024. PMID: 39457055 Free PMC article.
-
Mechanistic Investigation into Copper(I) Hydride Catalyzed Formic Acid Dehydrogenation.ACS Catal. 2024 Oct 7;14(20):15599-15608. doi: 10.1021/acscatal.4c05008. eCollection 2024 Oct 18. ACS Catal. 2024. PMID: 39444528 Free PMC article.
-
Luminescent Properties of β-(hydroxyaryl)-butenolides and Fluorescence Quenching in Water.J Fluoresc. 2024 Jan 9. doi: 10.1007/s10895-023-03546-z. Online ahead of print. J Fluoresc. 2024. PMID: 38193954
-
Selectivity control in thiol-yne click reactions via visible light induced associative electron upconversion.Chem Sci. 2020 Jul 23;11(37):10061-10070. doi: 10.1039/d0sc01939a. Chem Sci. 2020. PMID: 34094267 Free PMC article.
-
Switchable protection and exposure of a sensitive squaraine dye within a redox active rotaxane.Commun Chem. 2024 Oct 4;7(1):229. doi: 10.1038/s42004-024-01312-1. Commun Chem. 2024. PMID: 39367250 Free PMC article.
LinkOut - more resources
Full Text Sources
Other Literature Sources
Research Materials
Miscellaneous