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Spherically averaged versus angle-dependent interactions in quadrupolar fluids.

par Mognetti, Bortolo Matteo ;Oettel, M;Yelash, L;Virnau, P;Paul, William;Binder, K.
Référence Physical review. E, Statistical, nonlinear, and soft matter physics, 77, 4 Pt 1, page (041506)
Publication Publié, 2008-04

Article révisé par les pairs

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Résumé :

Employing simplified models in computer simulation is on the one hand often enforced by computer time limitations but on the other hand it offers insights into the molecular properties determining a given physical phenomenon. We employ this strategy to the determination of the phase behavior of quadrupolar fluids, where we study the influence of omitting angular degrees of freedom of molecules via an effective spherically symmetric potential obtained from a perturbative expansion. Comparing the liquid-vapor coexistence curve, vapor pressure at coexistence, interfacial tension between the coexisting phases, etc., as obtained from both the models with the full quadrupolar interactions and the (approximate) isotropic interactions, we find discrepancies in the critical region to be typically (such as in the case of carbon dioxide) of the order of 4%. However, when the Lennard-Jones parameters are rescaled such that critical temperatures and critical densities of both models coincide with the experimental results, almost perfect agreement between the above-mentioned properties of both models is obtained. This result justifies the use of isotropic quadrupolar potentials. We also present a detailed comparison of our simulations with a combined integral equation-density functional approach and show that the latter provides an accurate description except for the vicinity of the critical point.