Integral equation study of a Stockmayer fluid adsorbed in polar disordered matrices.

Abstract

Based on replica integral equations in the (reference) hypernetted chain approximation we investigate the structural features and phase properties of a dipolar Stockmayer fluid confined to a disordered dipolar matrix. The integral equations are applied to the homogeneous high-temperature phase where the system is globally isotropic. At low densities we find the influence of dipolar interactions between fluid (f) and matrix (m) particles to be surprisingly similar to the previously investigated effect of attractive isotropic (fm) interactions: the critical temperature of the vapor-liquid transition decreases with increasing (fm) coupling, while the critical density increases. The anisotropic nature of the dipolar (fm) interactions turns out to play a more dominant role at high fluid densities where we observe a pronounced sensitivity in the dielectric constant and a strong degree of local orientational ordering of the fluid particles along the local fields generated by the matrix. Moreover, an instability of the dielectric constant, which is a precursor of ferroelectric ordering occurring both in bulk Stockmayer fluids and in fluids in nonpolar matrices, is observed only for very small dipolar (fm) couplings.