Polarization model for water and its ionic dissociation products

In order to achieve a simple description of aggregates of deformable water molecules, a new model has been constructed which treats H+ and O2− particles as the basic dynamical and structural elements. The H+ units are bare protons, while the O2− units possess a form of nonlocal polarizability consistent with their electronic structure. The model yields water molecules which have the correct geometry and dipole moment, and which engage in hydrogen bonding to one another. Minimum‐energy structures have been determined for the water dimer and trimer and for small hydrate clusters of H+ and OH−; comparison with relevant experiments and quantum–mechanical calculations is satisfactory.

[1]  A. G. Harrison,et al.  ENERGETICS AND MECHANISM OF HYDRONIUM ION FORMATION BY ELECTRON IMPACT , 1963 .

[2]  J. A. Barker,et al.  Structure of water; A Monte Carlo calculation , 1969 .

[3]  E. Clementi,et al.  Study of the structure of molecular complexes. IV. The Hartree‐Fock potential for the water dimer and its application to the liquid state , 1973 .

[4]  H. Scheraga,et al.  Water molecule interactions. Stability of cyclic polymers , 1973 .

[5]  J. S. Rowlinson,et al.  The lattice energy of ice and the second virial coefficient of water vapour , 1951 .

[6]  F. Stillinger,et al.  Improved simulation of liquid water by molecular dynamics , 1974 .

[7]  Jules W. Moskowitz,et al.  Water Molecule Interactions , 1970 .

[8]  D. Smith,et al.  Anharmonic force constants of water , 1972 .

[9]  G. Diercksen,et al.  SCF-CI studies of correlation effects on hydrogen bonding and ion hydration , 1975 .

[10]  H. Preuss,et al.  Wellenmechanische Absolutrechnungen an Moleklen und Atomsystemen mit derSCF?MO?LC(LCGO) Methode. XI. Das Hydroxylanion (OH)? , 1967 .

[11]  M. Allavena,et al.  Semi-empirical calculations on the structure of the oxonium ion in various crystal sites and relative acidity scale , 1976 .

[12]  M. Eigen,et al.  Self-dissociation and protonic charge transport in water and , 1958, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[13]  F. Stillinger.  Theoretical approaches to the intermolecular nature of water. , 1977, Philosophical transactions of the Royal Society of London. Series B, Biological sciences.

[14]  F. Stillinger,et al.  Study of a central force model for liquid water by molecular dynamics , 1975 .

[15]  M. Newton,et al.  Ab initio studies on the structures and energetics of inner- and outer-shell hydrates of the proton and the hydroxide ion , 1971 .

[16]  M. Arshadi,et al.  Solvation of the hydrogen ion by water molecules in the gas phase. Heats and entropies of solvation of individual reactions. H+(H2O)n-1 + H2O .fwdarw. H+(H2O)n , 1967 .

[17]  John S. Muenter,et al.  Electric dipole moments of low J states of H2O and D2O , 1973 .

[18]  Felix Franks,et al.  Water:A Comprehensive Treatise , 1972 .

[19]  L. Friedman,et al.  Experimental Study of Heat of Proton Solvation , 1968 .

[20]  I. Olovsson.  Hydrogen‐Bond Studies. XXIX. Crystal Structure of Perchloric Acid Dihydrate, H5O2+ClO4− , 1968 .

[21]  John S. Muenter,et al.  THE STRUCTURE OF WATER DIMER FROM MOLECULAR BEAM ELECTRIC RESONANCE SPECTROSCOPY: PARTIALLY DEUTERATED DIMERS , 1977 .

[22]  F. Stillinger,et al.  Central-force model for liquid water , 1975 .

[23]  Frank H. Stillinger,et al.  Revised central force potentials for water , 1978 .

[24]  F. Stillinger.  Effective Pair Interactions in Liquids. Water , 1970 .

[25]  Walter Kauzmann,et al.  The Structure and Properties of Water , 1969 .

[26]  J. Beauchamp,et al.  Proton Affinities of H2S and H2O , 1968 .

[27]  F. Stillinger.  Density Expansions for Effective Pair Potentials , 1972 .