A mean field theory for fluids of multipolar particles in contact with a polarizable wall

Fluids of multipolar particles in contact with a semi-infinite polarizable hard wall are considered. A mean field theory which reduces the many-body electrostatic wall–solvent interactions to an effective pair potential is described. The effective potential can be employed in conjunction with the reference hypernetted-chain approximation, or some other integral equation theory, to obtain a self-consistent solution for the wall–solvent correlation function and hence the solvent structure at the interface. Explicit results are given for dipolar hard sphere fluids in contact with walls having dielectric constants ranging from 1 to ∞. For this system, it is shown that contributions to the wall–solvent potential from images of other particles are very important and act strongly against the direct ‘‘self-image’’ interaction.