Fluids of polarizable hard spheres with dipoles and tetrahedral quadrupoles Integral equation results with application to liquid water

Abstract

The mean spherical, linearized hypernetted chain and quadratic hypernetted chain approximations are solved for a fluid of hard spheres with embedded point dipoles and tetrahedral quadrupoles and this system is shown to be quite similar to the dipole-linear quadrupole case previously studied. However, tetrahedral quadrupoles have a larger influence upon the structural and thermodynamic properties and are slightly more effective in decreasing the dielectric constant from the purely dipolar value. Also we describe a simple self-consistent mean field theory which allows molecular polarizability to be taken into account. This approximation together with the integral equation methods is applied to a polarizable dipole-tetrahedral quadrupole fluid with water-like parameters. The dielectric constant of this system is found to be in good agreement with the experimental results for liquid water for temperatures ranging from 25°C to 300°C. The influence of molecular polarizability is shown to be very large. At 25°C the mean dipole moment is ∼2·56 D compared with ∼1·85 D in the gas phase and the dielectric constant increases from ∼25 for non-polarizable particles to ∼80 for the polarizable model.