Abstract
No modern theory of polymer excluded volume adequately describes the crossover from poor solvent to good solvent conditions; a fundamental difficulty is a singularity in the binary cluster integral. Mayer expansion techniques are applied to a model with a pair interaction between monomers to clarify the distinction between “geometric” and “solvent” contributions to excluded volume. Detailed calculations are undertaken for a hard-core potential and a mimic Lennard-Jones potential. The significance of the singularity in the binary cluster integral for calculations in the crossover regime is discussed.
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