Journal of Chemical Physics, Vol.105, No.10, 4323-4341, 1996
Self-Consistent Integral-Equation Theory of Chain-Molecular Liquids .2. Improved Intermolecular Equations
Improved self-consistent intermolecular integral equations for a chain-molecular liquid are derived from the polymer Kirkwood hierarchy. The present work is a continuation of our recent work reported in a previous paper [J. Chem. Phys. 103, 2140 (1995)]. It is shown that the reference interaction site model (RISM) equation and extensions thereof can be obtained from the new intermolecular equations. The solutions of the new self-consistent set of intra- and intermolecular equations are compared with computer simulation data for chains with repulsive interaction potentials whose lengths N vary from 4 to 100 sites. The intermolecular correlation functions obtained from simulations are accurately reproduced. Comparisons with simulation data for the pressure equation of state and excess chemical potential show that the predictions of the self-consistent theory are accurate for packing fractions up to 0.4. These thermodynamic functions are found to scale as N for N > 16, implying that results obtained for short chains can be extrapolated to much longer chains.
Keywords:MONTE-CARLO SIMULATIONS;GREEN-YVON EQUATION;POLYMERIC LIQUIDS;FLUIDS;APPROXIMATION;PRESSURE;MELTS