Spherically averaged versus angle-dependent interactions in quadrupolar fluids.pdf

Spherically averaged versus angle-dependent interactions in quadrupolar fluids B. M. Mognetti, M. Oettel, L. Yelash, P. Virnau, W. Paul and K. Binder 8 0 Institut f¨ur Physik, Johannes Gutenberg–Universit¨at Mainz, 0 2 Staudinger Weg 7, D-55099 Mainz r a M Employing simplified models in computer simulation is on the one hand often en- 5 forced by computer time limitations but on the other hand it offers insights into 2 ] the molecular properties determining a given physical phenomenon. We employ this h c strategy to the determination of the phase behaviour of quadrupolar fluids, where e m we study the influence of omitting angular degrees of freedom of molecules via an - t a effective spherically symmetric potential obtained from a perturbative expansion. t s . Comparing the liquid-vapor coexistence curve, vapor pressure at coexistence, inter- t a m facial tension between the coexisting phases, etc., as obtained from both the models - d with the full quadrupolar interactions and the (approximate) isotropic interactions, n o we find discrepancies in the critical region to be typically (such as in the case of c [ carbon dioxide) of the order of 4%. However, when the Lennard-Jones parameters 1 v are rescaled such that critical temperatures and critical densities of both models 7 0 coincide with the experimental results, almost perfect agreement between the above- 5 3 mentioned properties of both models is obtained.