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Abstract
The Gibbs-Duhem integration scheme is combined with the osmotic Gibbs-ensemble simulation method presented in previous work [Brennan, J.K. and Madden, W.G. "Phase coexistence curves for off-lattice polymer-solvent mixtures: Gibbs-ensemble simulations." Macromolecules , 2002, 35, 2827.] to calculate the phase coexistence of a polymer-solvent mixture. Gibbs-Duhem integration simulations are carried out at temperatures for which the osmotic Gibbs-ensemble method is not valid because the solvent-rich phase contains a significant amount of polymer. This combined strategy allows for the calculation of the full coexistence curve for polymer-solvent systems in the continuum. An alternative formulation of the Gibbs-Duhem integration algorithm is also presented. A major strength of the technique is that neither chain insertions nor deletions are required. The method allows for the calculation of the phase behavior of polymer-solvent mixtures containing long chains or branched and networked chains not previously possible.