FUSED HARD-SPHERE CHAIN MOLECULES - COMPARISON BETWEEN MONTE-CARLO SIMULATION FOR THE BULK PRESSURE AND GENERALIZED FLORY THEORIES

We report Monte Carlo simulation results for the bulk pressure of fused-hard-sphere (FHS) chain fluids with bond-length-to-bead-diameter ratios ≈ 0.4 at chain lengths n 4, 8 and 16. We also report density profiles for FHS chain fluids at a hard wall. The results for the compressibility factor are compared to results from extensions of the Generalized Flory (GF) and Generalized Flory Dimer (GFD) theories proposed by Yethiraj et al. and by us. Our new GF theory, GF-AB, significantly improves the prediction of the bulk pressure of fused-hard-sphere chains over the GFD theories proposed by Yethiraj et al. and by us although the GFD theories give slightly better low-density results. The GFD-A theory, the GFD-B theory and the new theories (GF-AB, GFD-AB, and GFD-AC) satisfy the exact zero-bonding-length limit. All theories considered recover the GF or GFD theories at the tangent hard-sphere chain limit. © 1995 American Institute of Physics.