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Reference interaction site model and molecular dynamics study of structure and thermodynamics of methanol.

Costa D, Munaó G, Saija F, Caccarno C

Dipartimento di Fisica, Università di Messina, Contrada Papardo, 98166 Messina, Italy and CNISM, Contrada Papardo, 98166 Messina, Italy.

Thermodynamic and structural properties of various models of liquid methanol are investigated in the framework provided by the reference interaction site model (RISM) theory of molecular fluids. The theoretical predictions are systematically compared with molecular dynamics simulations both at ambient conditions and along a few supercritical isotherms. RISM results for the liquid-vapor phase separation are also obtained and assessed against available Gibbs ensemble Monte Carlo data. At ambient conditions, the theoretical correlations weakly depend on the specific details of the molecular models and reproduce the simulation results with different degrees of accuracy, depending on the pair of interaction sites considered. The position and the strength of the hydrogen bond are quite satisfactorily predicted. RISM results for the internal energy are almost quantitative whereas the pressure is generally overestimated. As for the liquid-vapor phase coexistence, RISM predictions for the vapor branch and for the critical temperature are quite accurate; on the other side, the liquid branch densities, and consequently the critical density, are underestimated. We discuss our results in terms of intrinsic limitations, and suitable improvements, of the RISM approach in describing the physical properties of polar fluids, and in the perspective of a more general investigation of mixtures of methanol with nonpolar fluids of specific interest in the physics of associating fluids.

Published 17 December 2007 in J Chem Phys, 127(22): 224501.
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