Flory theory revisited

Abstract

The Flory theory for a single polymer chain is derived as the lowest order of a cumulant expansion. In this approach, the full original Flory free energy (including the logarithmic term), is recovered. %This term does not change the wandering exponent $ ν$ but turns out to %be responsible for the crossover from Brownian $ (d>4) $ to swollen $ %(d\leq4) $ %regime. The prefactors of the elastic and repulsive energy are calculated from the microscopic parameters. The method can be applied to other types of monomer-monomer interactions, and the case of a single chain in a bad solvent is discussed . The method is easily generalized to many chain systems (polymers in solutions), yielding the usual crossovers with chain concentration. Finally, this method is suitable for a systematic expansion around the Flory theory. The corrections to Flory theory consist of extensive terms (proportional to the number $N$ of monomers) and powers of $N^{2-νd}$ . These last terms diverge in the thermodynamic limit, but less rapidly than the usual Fixman expansion in $N^{2- d/2}$.