The effects of charge transfer on the aqueous solvation of ions.

Ab initio-based charge partitioning of ionic systems results in ions with non-integer charges. This charge-transfer (CT) effect alters both short- and long-range interactions. Until recently, the effects of CT have been mostly neglected in molecular dynamics (MD) simulations. The method presented in this paper for including charge transfer between ions and water is consistent with ab initio charge partitioning and does not add significant time to the simulation. The ions of sodium, potassium, and chloride are parameterized to reproduce dimer properties and aqueous structures. The average charges of the ions from MD simulations (0.900, 0.919, and -0.775 for Na(+), K(+), and Cl(-), respectively) are consistent with quantum calculations. The hydration free energies calculated for these ions are in agreement with experimental estimates, which shows that the interactions are described accurately. The ions also have diffusion constants in good agreement with experiment. Inclusion of CT results in interesting properties for the waters in the first solvation shell of the ions. For all ions studied, the first shell waters acquire a partial negative charge, due to the difference between water-water and water-ion charge-transfer amounts. CT also reduces asymmetry in the solvation shell of the chloride anion, which could have important consequences for the behavior of chloride near the air-water interface.

[1]  Sandeep Patel,et al.  Hydration free energies of monovalent ions in transferable intermolecular potential four point fluctuating charge water: an assessment of simulation methodology and force field performance and transferability. , 2007, The Journal of chemical physics.

[2]  S. Atlas,et al.  An empirical charge transfer potential with correct dissociation limits. , 2003, The Journal of chemical physics.

[3]  L. Roncaratti,et al.  Charge-transfer energy in the water-hydrogen molecular aggregate revealed by molecular-beam scattering experiments, charge displacement analysis, and ab initio calculations. , 2010, Journal of the American Chemical Society.

[4]  Marvin Johnson,et al.  Isolating the Charge-Transfer Component of the Anionic H Bond Via Spin Suppression of the Intracluster Proton Transfer Reaction in the NO-·H2O Entrance Channel Complex† , 2002 .

[5]  M. Tissandier,et al.  The Proton's Absolute Aqueous Enthalpy and Gibbs Free Energy of Solvation from Cluster-Ion Solvation Data , 1998 .

[6]  P. Procacci,et al.  Polarization response of water and methanol investigated by a polarizable force field and density functional theory calculations: implications for charge transfer. , 2005, The Journal of chemical physics.

[7]  Boris M. Smirnov,et al.  Reference Data on Atoms, Molecules, and Ions , 1985 .

[8]  Jonas Boström,et al.  A NEMO potential that includes the dipole–quadrupole and quadrupole–quadrupole polarizability , 2010, J. Comput. Chem..

[9]  Alexander D. MacKerell,et al.  Simulating Monovalent and Divalent Ions in Aqueous Solution Using a Drude Polarizable Force Field. , 2010, Journal of chemical theory and computation.

[10]  Determination of the charge profile in the KcsA selectivity filter using ab initio calculations and molecular dynamics simulations. , 2009, Physical chemistry chemical physics : PCCP.

[11]  P. Kebarle,et al.  Hydration of the alkali ions in the gas phase. Enthalpies and entropies of reactions M+(H2O)n-1 + H2O = M+(H2O)n , 1970 .

[12]  L. Renee Olano,et al.  Fluctuating charge normal modes: An algorithm for implementing molecular dynamics simulations with polarizable potentials , 2005, J. Comput. Chem..

[13]  W. Howells,et al.  Chloride ions in aqueous solutions , 1980, Nature.

[14]  M. Plesset,et al.  Note on an Approximation Treatment for Many-Electron Systems , 1934 .

[15]  Norman H. Tolk,et al.  Extended Hückel theory for ionic molecules and solids: An application to alkali halides , 1988 .

[16]  Gerhard Hummer,et al.  System-Size Dependence of Diffusion Coefficients and Viscosities from Molecular Dynamics Simulations with Periodic Boundary Conditions , 2004 .

[17]  J. Hynes,et al.  Frequency Shifts in the Hydrogen-Bonded OH Stretch in Halide−Water Clusters. The Importance of Charge Transfer , 2000 .

[18]  Steven W. Rick,et al.  The effects of charge transfer on the properties of liquid water. , 2011, The Journal of chemical physics.

[19]  C. Hardacre,et al.  Application of static charge transfer within an ionic-liquid force field and its effect on structure and dynamics. , 2008, Chemphyschem : a European journal of chemical physics and physical chemistry.

[20]  Steven J. Stuart,et al.  Dynamical fluctuating charge force fields: Application to liquid water , 1994 .

[21]  P. Procacci,et al.  Comparing polarizable force fields to ab initio calculations reveals nonclassical effects in condensed phases. , 2005, The Journal of chemical physics.

[22]  L. Dang,et al.  MOLECULAR DYNAMICS STUDY OF WATER CLUSTERS, LIQUID, AND LIQUID-VAPOR INTERFACE OF WATER WITH MANY-BODY POTENTIALS , 1997 .

[23]  Claude Millot,et al.  Revised Anisotropic Site Potentials for the Water Dimer and Calculated Properties , 1998 .

[24]  M. Probst,et al.  On the performance of molecular polarization methods. II. Water and carbon tetrachloride close to a cation. , 2005, The Journal of chemical physics.

[25]  David E. Smith,et al.  Computer simulations of NaCl association in polarizable water , 1994 .

[26]  J. Leszczynski,et al.  Optimal methods for calculation of the amount of intermolecular electron transfer , 2002 .

[27]  S. Asher,et al.  Lowest energy electronic transition in aqueous Cl(-) salts: Cl(-) → (H2O)6 charge transfer transition. , 2011, The journal of physical chemistry. A.

[28]  Klaus R. Liedl,et al.  BORN-OPPENHEIMER AB INITIO QM/MM DYNAMICS SIMULATIONS OF NA+ AND K+ IN WATER : FROM STRUCTURE MAKING TO STRUCTURE BREAKING EFFECTS , 1998 .

[29]  M. Masia.  Ab initio based polarizable force field parametrization. , 2008, The Journal of chemical physics.

[30]  J. Banavar,et al.  Computer Simulation of Liquids , 1988 .

[31]  D. Rogers,et al.  Polarization and charge transfer in the hydration of chloride ions. , 2009, The Journal of chemical physics.

[32]  Alan Grossfield,et al.  Simulation of Ca2+ and Mg2+ solvation using polarizable atomic multipole potential. , 2006, The journal of physical chemistry. B.

[33]  M. Probst,et al.  Polarization damping in halide-water dimers , 2006 .

[34]  S. Varma,et al.  Multibody effects in ion binding and selectivity. , 2010, Biophysical journal.

[35]  T. H. Dunning.  Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .

[36]  Nohad Gresh,et al.  Toward a Separate Reproduction of the Contributions to the Hartree-Fock and DFT Intermolecular Interaction Energies by Polarizable Molecular Mechanics with the SIBFA Potential. , 2007, Journal of chemical theory and computation.

[37]  J. Korchowiec,et al.  New energy partitioning scheme based on the self-consistent charge and configuration method for subsystems: Application to water dimer system , 2000 .

[38]  D. Tobias,et al.  Surface Effects on Aqueous Ionic Solvation: A Molecular Dynamics Simulation Study of NaCl at the Air/Water Interface from Infinite Dilution to Saturation , 2000 .

[39]  Andrew S. Dixon,et al.  Charge-Transfer Interactions in Macromolecular Systems: A New View of the Protein/Water Interface , 1998 .

[40]  Ioannis Skarmoutsos,et al.  On Ion and Molecular Polarization of Halides in Water. , 2009, Journal of chemical theory and computation.

[41]  S. Varma,et al.  Coordination numbers of alkali metal ions in aqueous solutions. , 2006, Biophysical chemistry.

[42]  R. Bader.  Atoms in molecules : a quantum theory , 1990 .

[43]  Pavel Jungwirth,et al.  Specific ion effects at the air/water interface. , 2006, Chemical reviews.

[44]  Piotr Cieplak,et al.  Polarization effects in molecular mechanical force fields , 2009, Journal of physics. Condensed matter : an Institute of Physics journal.

[45]  Kenneth D Jordan,et al.  A second generation distributed point polarizable water model. , 2010, The Journal of chemical physics.

[46]  C. Cramer,et al.  Polarization Effects in Aqueous and Nonaqueous Solutions. , 2007, Journal of chemical theory and computation.

[47]  Steven J. Stuart,et al.  Effects of Polarizability on the Hydration of the Chloride Ion , 1996 .

[48]  Ursula Rothlisberger,et al.  Polarization effects and charge transfer in the KcsA potassium channel. , 2006, Biophysical chemistry.

[49]  Benoît Roux,et al.  Modeling induced polarization with classical Drude oscillators: Theory and molecular dynamics simulation algorithm , 2003 .

[50]  G. Henkelman,et al.  A grid-based Bader analysis algorithm without lattice bias , 2009, Journal of physics. Condensed matter : an Institute of Physics journal.

[51]  Matteo Dal Peraro,et al.  Solute-solvent charge transfer in aqueous solution. , 2005, Chemphyschem : a European journal of chemical physics and physical chemistry.

[52]  K. Honda.  An effective potential function with enhanced charge-transfer-type interaction for hydrogen-bonding liquids , 2002 .

[53]  K. Merz,et al.  Charge transfer in small hydrogen bonded clusters , 2002 .

[54]  Han Myoung Lee,et al.  Comparative ab initio study of the structures, energetics and spectra of X−⋅(H2O)n=1–4 [X=F, Cl, Br, I] clusters , 2000 .

[55]  A. V. Duin,et al.  ReaxFF: A Reactive Force Field for Hydrocarbons , 2001 .

[56]  Incidence of partial charges on ion selectivity in potassium channels. , 2006, The Journal of chemical physics.

[57]  Pengyu Y. Ren,et al.  Ion solvation thermodynamics from simulation with a polarizable force field. , 2003, Journal of the American Chemical Society.

[58]  Tjerk P. Straatsma,et al.  NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations , 2010, Comput. Phys. Commun..

[59]  L. Delle Site,et al.  Ionic charge reduction and atomic partial charges from first-principles calculations of 1,3-dimethylimidazolium chloride. , 2010, The journal of physical chemistry. B.

[60]  C. David.  A variable charge central force model for water and its ionic dissociation products , 1996 .

[61]  L. Pacios,et al.  Variation with the intermolecular distance of properties dependent on the electron density in hydrogen bond dimers , 2001 .

[62]  Jiahao Chen,et al.  QTPIE: Charge transfer with polarization current equalization. A fluctuating charge model with correct asymptotics , 2007, 0807.2068.

[63]  C. Wick.  Electrostatic dampening dampens the anion propensity for the air-water interface. , 2009, The Journal of chemical physics.

[64]  R. C. Cohen,et al.  Effects of cations on the hydrogen bond network of liquid water: new results from X-ray absorption spectroscopy of liquid microjets. , 2006, The journal of physical chemistry. B.

[65]  Suyong Re,et al.  Charge transfer and OH vibrational frequency red shifts in nitrate-water clusters. , 2008, The journal of physical chemistry. A.