Wertheim and Bjerrum-Tani-Henderson theories for associating fluids: a critical assessment

Abstract

Two theories for associating fluids recently used to study clustering in models for self-assembling patchy particles, Wertheim's and Bjerrum-Tani-Henderson theories, are carefully compared. We show that, for a fluid allowing only for dimerization, Wertheim theory is equivalent to the Bjerrum-Tani-Henderson theory neglecting intercluster correlations. Nonetheless, while the former theory is able to account for percolation and condensation, the latter is not. For the Bjerrum-Tani-Henderson theory we also rigorously prove the uniqueness of the solution for the cluster's concentrations and the reduction of the system of equations to a single one for a single unknown. We carry out Monte Carlo simulations of two simple models of dimerizing fluids and compare quantitatively the predictions of the two theories with the simulation data.

arXiv comment21 pages, 6 figures

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Cited by in corpus (4)

• Wertheim perturbation theory: thermodynamics and structure of patchy colloids
• The moment sum-rules for ionic liquids at criticality
• Effect of quantum dispersion on the radial distribution function of a one-component sticky-hard-sphere fluid
• Andersen-Weeks-Chandler perturbation theory and one-component sticky-hard-spheres