Solution of the Percus-Yevick equation for square well spherocylinders.
The Percus-Yevick equation for square-well spherocylinders has been numerically solved for some selected orientations following a methodology proposed previously for different fluids of elongated molecules. The equation is solved for particles of aspect ratios ranging from L/sigma=0.3 up to L/sigma=5.0, attractive range lambda/sigma=1.5, and packing fractions within eta=0.1-0.3. The resulting pair correlation functions are checked against isothermal-isobaric Monte Carlo simulations and good agreement is found for the short-range structure, at intermolecular distances within one molecular diameter sigma to contact for each of the selected orientations. At larger distances, the integral equation tends to overestimate the pair correlations. The results confirm the prediction of reference-system average Mayer-function perturbation theory for short aspect ratios, reaching the Onsager limit for the greater aspect ratios. Some instabilities of the solution for the longest models and higher densities are tentatively discussed in terms of their possible relation to frustration phenomena found in some polymer and complex systems.
Martínez-Haya
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Departamento de Ciencias Ambientales, Facultad de Ciencias Experimentales, Universidad Pablo de Olavide, Ctra. de Utrera Km 1, 41013 Seville, Spain. bmarhay@dex.upo.es
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Lago
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