Free Energies in the Landau and Molecular Field Approaches

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Abstract
An expression for the entropy as a power series in the order parameter is derived in the context of molecular field theory. The expression is valid both at and away from equilibrium. It is a unique generalization of molecular field theory to non-equilibrium situations. Discrepancies with certain expressions which have appeared in the literature are resolved. Analysis of the radius of convergence of the power series indicates that in certain cases, including the Maier-Saupe model of liquid crystals, molecular field theory and Landau theory cannot be made to agree over the entire range of possible values of the order parameter.