Electrical properties of polarizable ionic solutions. II. Computer simulation results

We present molecular dynamics simulations for two limiting models of ionic solutions: one where the solvent molecules are polar, but nonpolarizable; the other where they are only polarizable (but have no permanent dipole moment). For both models, the static two‐body correlation functions, the frequency‐dependent dielectric constant and conductivity are calculated and the statistical uncertainty on these quantities estimated for molecular dynamics runs of the order of 105 integration steps. For the case of the polar solvent, the accuracy of the computed static interionic correlation functions allows a valuable test of the hypernetted chain integral equation theory at an ionic concentration of 0.04. The quantitative variation of the fluctuations of polarization and electrical current with change of boundary conditions is evaluated within the context of the second model (polarizable nonpolar solvent). Applying the relationships derived in Part I between the phenomenological coefficients and susceptibilities,...

[1]  D. Lévesque,et al.  Electrical properties of polarizable ionic solutions. I. Theoretical aspects , 1989 .

[2]  S. Yip,et al.  Molecular dynamics simulation of the concentration-dependent dielectric constants of aqueous nacl solutions , 1988 .

[3]  D. Lévesque,et al.  A comparison between computer simulation and theoretical results for ionic solutions , 1987 .

[4]  R. Rentsch,et al.  On the dielectric susceptibility of classical Coulomb systems. II , 1987 .

[5]  D. Lévesque,et al.  Theoretical calculation of ionic solution properties , 1986 .

[6]  Martin Neumann,et al.  Dielectric relaxation in water. Computer simulations with the TIP4P potential , 1986 .

[7]  Martin Neumann,et al.  Consistent calculation of the static and frequency-dependent dielectric constant in computer simulations , 1984 .

[8]  O. Steinhauser,et al.  On the calculation of the frequency-dependent dielectric constant in computer simulations , 1983 .

[9]  G. N. Patey,et al.  Static dielectric properties of polarizable Stockmayer fluids , 1981 .

[10]  C. C. Wright,et al.  Boundary conditions for Monte Carlo simulation of charged systems , 1981 .

[11]  John W. Perram,et al.  Computer simulation of ionic systems. Influence of boundary conditions , 1981 .

[12]  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.

[13]  Franz J. Vesely,et al.  N-particle dynamics of polarizable Stockmayer-type molecules , 1977 .

[14]  M. Neumann.  Computer simulation and the dielectric constant at finite wavelength , 1986 .

[15]  Lévesque,et al.  Low-density phase diagram of the two-dimensional Coulomb gas. , 1986, Physical review. B, Condensed matter.

[16]  Hubert Cachet,et al.  Relaxation diélectrique de solutions de bromure de tétra-n-butylammonium dans le tétrachlorure de carbone , 1974 .