Journal of Chemical Physics, Vol.118, No.8, 3628-3638, 2003
Phase behavior of Stockmayer fluids confined to a nonpolar porous material
The phase behavior of hard core Stockmayer fluids (i.e., dipolar hard spheres with additional Lennard-Jones interactions) adsorbed into a disordered porous hard sphere matrix is studied by means of replica-integral equations in the reference hypernetted chain approximation. The integral equations are solved for the homogeneous isotropic phase and the low-temperature phase behavior is inferred from those thermal fluctuations which strongly increase when the stability limit of the isotropic phase is approached. Analyzing first number density fluctuations and adsorption isotherms we find that the vapor-liquid transition occuring in bulk Stockmayer fluids still takes place in matrices of sufficiently high porosity. The corresponding critical point is shifted towards a lower temperature and density, in agreement with previous results on simpler fluids. At high fluid densities a diverging dielectric constant indicates the presence of an isotropic-to-ferroelectric transition for all systems considered, and the corresponding transition temperatures are found to increase with increasing matrix density. Comparing the fluid-matrix systems with fully equilibrated mixtures we argue that this enhanced tendency for ferroelectric ordering is essentially due to excluded volume effects. (C) 2003 American Institute of Physics.