APPLICATION OF GRAPH THEORY TO THE STATISTICAL THERMODYNAMICS OF LATTICE POLYMERS .1. ELEMENTS OF THEORY AND TEST FOR DIMERS

摘要

The lattice cluster theory (LCT) is extended to enable inclusion of longer range correlation contributions to the partition function of lattice model polymers in the athermal limit. A diagrammatic technique represents the expansion of the partition function in powers of the inverse lattice coordination number. Graph theory is applied to sea, classify, and evaluate the numerous diagrams appearing in higher orders. New general theorems are proven that provide a significant reduction in the computational labor required to evaluate the contributions from higher order correlations. The new algorithm efficiently generates the correction to the Flory mean held approximation from as many as eight sterically interacting bonds. While the new results contain the essential ingredients for treating a system of flexible chains with arbitrary lengths and concentrations, the complexity of our new algorithm motivates us to test the theory here for the simplest case of a system of lattice dimers by comparison to the dimer packing entropies from the work of Gaunt. This comparison demonstrates that the eight bond LCT is exact through order phi(5) for dimers in one through three dimensions, where phi is the volume fraction of dimers. A subsequent work will use the contracted diagrams, derived and tested here, to treat the packing entropy for a system of flexible N-mers at a volume faction of phi on hypercubic lattices. (C) 1996 American Institute of Physics. [References: 51]