A polarizable, dissociating molecular dynamics model for liquid water

We describe a molecular dynamics model for dissociable, polarizable water. The model, which describes both the static and dynamic properties of real water quite reasonably, contains the following features: Self‐consistent local fields are calculated in an extension of an earlier algorithm in which the dipole moments of the water are treated as dynamical variables. An intramolecular three‐body potential assures that the molecular properties of water are in agreement with experiment. Ewald methods are used to take account of monopole–dipole and dipole–dipole as well as monopole–monopole interactions. The model was optimized using a Monte Carlo procedure in the parameter space which is described.

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

[2]  J. W. Halley,et al.  Molecular dynamics studies of complexing in binary molten salts with polarizable anions: MAX4 , 1988 .

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

[4]  L. Curtiss,et al.  Many-body effects in ion-water interactions: Fe3+ in water , 1989 .

[5]  Mauro Ferrario,et al.  Constant pressure-constant temperature molecular dynamics for rigid and partially rigid molecular systems , 1985 .

[6]  P. Bunker,et al.  A preliminary determination of the equilibrium geometry and inversion potential in H3O+ from experiment , 1984 .

[7]  F. Stillinger,et al.  Study of the water octamer using the polarization model of molecular interactions , 1980 .

[8]  J. A. C. Rullmann,et al.  A polarizable water model for calculation of hydration energies , 1988 .

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

[10]  Rahman,et al.  Molecular-dynamics study of atomic motions in water. , 1985, Physical review. B, Condensed matter.

[11]  Terry P. Lybrand,et al.  A new water potential including polarization: Application to gas‐phase, liquid, and crystal properties of water , 1990 .

[12]  D. Lévesque,et al.  Computer simulation and theoretical results for a polar-polarizable fluid , 1985 .

[13]  G. Wilse Robinson,et al.  A new flexible/polarizable water model , 1991 .

[14]  Frank H. Stillinger,et al.  Polarization model for water and its ionic dissociation products , 1978 .

[15]  J. E. Quinn,et al.  Cooperative effects in simulated water , 1979, Nature.

[16]  J. Perram,et al.  Simulation of electrostatic systems in periodic boundary conditions. I. Lattice sums and dielectric constants , 1980, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[17]  Warren J. Hehre,et al.  AB INITIO Molecular Orbital Theory , 1986 .

[18]  Michiel Sprik,et al.  A polarizable model for water using distributed charge sites , 1988 .

[19]  J. Max.  Méthodes et techniques de traitement du signal et application aux mesures physiques. Tome 2 , 1981 .

[20]  Alan K. Soper,et al.  A new determination of the structure of water at 25°C , 1986 .

[21]  J. Price,et al.  Vibrational spectroscopy of the hydrated hydronium cluster ions H3O+·(H2O)n (n=1, 2, 3) , 1989 .

[22]  John W. Perram,et al.  The Physics of Superionic Conductors and Electrode Materials , 1985, July 1.

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