Predicting hydration energies for multivalent ions

We have predicted the free energy of hydration for 40 monovalent and multivalent cations and anions using density functional theory and the implicit solvent model COnductor like Screening MOdel for Real Solvents (COSMO‐RS) at the Becke‐Perdew (BP)/Triple zeta valence with polarization functions (TZVP) level. Agreement with experimental data for monovalent and divalent ions is good and shows no significant systematic errors. Predictions are noticeably better than with standard COSMO. The agreement with experimental data for trivalent and tetravalent ions is slightly worse and shows systematic errors. Our results indicate that quantum chemical calculations combined with COSMO‐RS solvent treatment is a reliable method for treating multivalent ions in solution, provided one hydration shell of explicit water molecules is included for metal cations. The accuracy is not high enough to allow absolute predictions of hydration energies but could be used to investigate trends for several ions, thanks to the low computational cost, in particular for ligand exchange reactions. © 2014 Wiley Periodicals, Inc.

[1]  F. Weigend.  Accurate Coulomb-fitting basis sets for H to Rn. , 2006, Physical chemistry chemical physics : PCCP.

[2]  V. S. Bryantsev,et al.  Calculation of solvation free energies of charged solutes using mixed cluster/continuum models. , 2008, The journal of physical chemistry. B.

[3]  B. Ninham,et al.  Specific ion effects: why DLVO theory fails for biology and colloid systems. , 2001, Physical review letters.

[4]  Florian Weigend,et al.  Auxiliary basis sets for main row atoms and transition metals and their use to approximate Coulomb potentials , 1997 .

[5]  D. Crerar,et al.  Migration of Radioactive Wastes: Radionuclide Mobilization by Complexing Agents , 1978, Science.

[6]  Marek Sierka,et al.  Fast evaluation of the Coulomb potential for electron densities using multipole accelerated resolution of identity approximation , 2003 .

[7]  Marco Häser,et al.  Auxiliary basis sets to approximate Coulomb potentials , 1995 .

[8]  Donald G Truhlar,et al.  Performance of SM6, SM8, and SMD on the SAMPL1 test set for the prediction of small-molecule solvation free energies. , 2009, The journal of physical chemistry. B.

[9]  M. Dozol,et al.  Radionuclide migration in groundwaters: Review of the behaviour of actinides (Technical Report) , 1993 .

[10]  D. Christianson,et al.  Catalysis by metal-activated hydroxide in zinc and manganese metalloenzymes. , 1999, Annual review of biochemistry.

[11]  Peter Deglmann,et al.  Thermodynamics of chemical reactions with COSMO‐RS: The extreme case of charge separation or recombination , 2012, J. Comput. Chem..

[12]  R L McNaughton,et al.  Electronic structure studies of oxomolybdenum tetrathiolate complexes: origin of reduction potential differences and relationship to cysteine-molybdenum bonding in sulfite oxidase. , 2000, Inorganic chemistry.

[13]  A. Klamt,et al.  COSMO : a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient , 1993 .

[14]  Andreas Klamt,et al.  Use of COSMO‐RS for the prediction of adsorption equilibria , 2002 .

[15]  A. Klamt,et al.  Fast solvent screening via quantum chemistry: COSMO‐RS approach , 2002 .

[16]  C. Peacock,et al.  Surface complexation model for multisite adsorption of copper(II) onto kaolinite , 2005 .

[17]  Andreas Klamt,et al.  First Principles Calculations of Aqueous pKa Values for Organic and Inorganic Acids Using COSMO-RS Reveal an Inconsistency in the Slope of the pKa Scale. , 2003, The journal of physical chemistry. A.

[18]  Hans W. Horn,et al.  Fully optimized contracted Gaussian basis sets for atoms Li to Kr , 1992 .

[19]  C. Cramer,et al.  A universal approach to solvation modeling. , 2008, Accounts of chemical research.

[20]  D. Sparks,et al.  Sulphate adsorption at the Fe (hydr)oxide–H2O interface: comparison of cluster and periodic slab DFT predictions , 2007 .

[21]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[22]  R. Lal,et al.  Soil structure and management: a review , 2005 .

[23]  A. Klamt,et al.  COSMO-RS: an alternative to simulation for calculating thermodynamic properties of liquid mixtures. , 2010, Annual review of chemical and biomolecular engineering.

[24]  D. Sparks,et al.  Quantum chemical study of arsenic (III, V) adsorption on Mn-oxides: implications for arsenic(III) oxidation. , 2009, Environmental science & technology.

[25]  Kathryn L. Nagy,et al.  Chemical weathering rate laws and global geochemical cycles , 1994 .

[26]  R. Franke,et al.  Alternative metals for homogeneous catalyzed hydroformylation reactions. , 2013, Angewandte Chemie.

[27]  G. Dyker.  Transition Metal Catalyzed Coupling Reactions under C-H Activation. , 1999, Angewandte Chemie.

[28]  Andreas Klamt,et al.  Blind prediction test of free energies of hydration with COSMO-RS , 2010, J. Comput. Aided Mol. Des..

[29]  A. Klamt,et al.  Refinement and Parametrization of COSMO-RS , 1998 .

[30]  Martin Andersson,et al.  How acidic is water on calcite , 2012 .

[31]  J. Perdew,et al.  Density-functional approximation for the correlation energy of the inhomogeneous electron gas. , 1986, Physical review. B, Condensed matter.

[32]  Sigurdur R. Gislason,et al.  Mineral Carbonation of CO2 , 2008 .

[33]  David A. Dixon,et al.  Absolute Hydration Free Energy of the Proton from First-Principles Electronic Structure Calculations , 2001 .

[34]  C. Hill,et al.  Homogeneous catalysis by transition metal oxygen anion clusters , 1995 .

[35]  M. Andersson,et al.  Sensitivity Analysis of Cluster Models for Calculating Adsorption Energies for Organic Molecules on Mineral Surfaces , 2011 .

[36]  J. Donoso,et al.  Theoretical calculations of stability constants and pKa values of metal complexes in solution: application to pyridoxamine-copper(II) complexes and their biological implications in AGE inhibition. , 2013, Physical chemistry chemical physics : PCCP.

[37]  Y. Shimoyama,et al.  Prediction of phase equilibria for mixtures containing water, hydrocarbons and alcohols at high temperatures and pressures by cubic equation of state with GE type mixing rule based on COSMO-RS , 2006 .

[38]  J. Tomasi,et al.  Modern Theories of Continuum Models , 2007 .

[39]  Andreas Klamt,et al.  Accurate prediction of basicity in aqueous solution with COSMO‐RS , 2006, J. Comput. Chem..

[40]  P. Tongying,et al.  A performance study of density functional theory with empirical dispersion corrections and spin-component scaled second-order Møller−Plesset perturbation theory on adsorbate–zeolite interactions , 2010 .

[41]  Yizhak Marcus,et al.  A simple empirical model describing the thermodynamics of hydration of ions of widely varying charges, sizes, and shapes , 1994 .

[42]  C. Zhan,et al.  First-Principles Determination of the Absolute Hydration Free Energy of the Hydroxide Ion† , 2002 .

[43]  Donald G Truhlar,et al.  SM6:  A Density Functional Theory Continuum Solvation Model for Calculating Aqueous Solvation Free Energies of Neutrals, Ions, and Solute-Water Clusters. , 2005, Journal of chemical theory and computation.

[44]  F. Weigend,et al.  Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. , 2005, Physical chemistry chemical physics : PCCP.

[45]  F. Neese,et al.  Theoretical bioinorganic chemistry: the electronic structure makes a difference. , 2007, Current opinion in chemical biology.

[46]  Maria João Ramos,et al.  The carboxylate shift in zinc enzymes: a computational study. , 2007, Journal of the American Chemical Society.

[47]  Hans W. Horn,et al.  ELECTRONIC STRUCTURE CALCULATIONS ON WORKSTATION COMPUTERS: THE PROGRAM SYSTEM TURBOMOLE , 1989 .

[48]  S. Buchwald,et al.  Biaryl phosphane ligands in palladium-catalyzed amination. , 2008, Angewandte Chemie.

[49]  A. Putnis.  Mineral replacement reactions: from macroscopic observations to microscopic mechanisms , 2002, Mineralogical Magazine.

[50]  S. Lago,et al.  Calculation of the absolute hydration enthalpy and free energy of H+ and OH− , 2000 .