Journal of Chemical Physics, Vol.103, No.16, 7166-7179, 1995
On the Equation of State for Thermal Polymer-Solutions and Melts
We measure the chemical potential in a polymer melt with a modification of Widom’s insertion method. Our method is based on partial insertion of a testchain by controlling the interaction between the testchain and the melt by means of a control parameter. The chemical potential can be obtained from a single run in a multicanonical-like simulation over a wide range of temperatures and densities. From the chemical potential the osmotic pressure and the entropy are calculated. We study a variant of the bond fluctuation model of a polymer melt where an energy is gained when the bond vector is taken from the set (+/-3,0,0) lattice spacings (or permutations thereof). From extensive previous studies it is known that the model exhibits a glass-like freezing at low temperatures. We show that the configurational entropy decreases strongly when one cools the system through this transition, but it remains distinctly nonzero in the glass phase.
Keywords:MONTE-CARLO SIMULATIONS;CHAIN MOLECULES;COMPUTER-SIMULATION;GLASS-TRANSITION;MACROMOLECULES;SCHEME;MODELS