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We consider the entropy of polydisperse chains placed on a lattice. In particular, we study a model for equilibrium polymerization, where the polydispersity is determined by two activities, for internal and endpoint monomers of a chain. We solve the problem exactly on a Husimi lattice built with squares and with arbitrary coordination number, obtaining an expression for the entropy as a function of the density of monomers and mean molecular weight of the chains. We compare this entropy with the one for the monodisperse case, and find that the excess of entropy due to polydispersity is identical to the one obtained for the one-dimensional case. Finally, we obtain a distribution of molecular weights with a rather complex behavior, but which becomes exponential for very large mean molecular weight of the chains, as required by scaling properties, which should apply in this limit.

Citation

Minos A Neto, Jürgen F Stilck. Entropy of polydisperse chains: solution on the Husimi lattice. The Journal of chemical physics. 2013 Jan 28;138(4):044902

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PMID: 23387620

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