Entropy of polydisperse chains: solution on the Bethe lattice

TL;DR

This paper derives an exact analytical expression for the entropy of polydisperse chains on a Bethe lattice, revealing how polydispersivity affects entropy and molecular weight distribution in equilibrium polymerization.

Contribution

It provides an exact solution for the entropy of polydisperse chains on a Bethe lattice, extending understanding of polymerization models with arbitrary coordination.

Findings

Entropy increases with polydispersivity, matching the 1D case.

Derived exponential molecular weight distribution.

Exact entropy expression for arbitrary coordination number.

Abstract

We consider the entropy of polydisperse chains placed on a lattice. In particular, we study a model for equilibrium polymerization, where the polydispersivity is determined by two activities, for internal and endpoint monomers of a chain. We solve the problem exactly on a Bethe lattice 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 polydispersivity is identical to the one obtained for the one-dimensional case. Finally, we obtain an exponential distribution of molecular weights.