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

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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.