Structural and hydrogen bond analysis for supercritical ethanol: A molecular simulation study

Monte Carlo simulations have been carried out to investigate supercritical ethanol using the OPLS-UA [W.L. Jorgensen, Optimized intermolecular potential functions for liquid alcohols, J. Phys. Chem. 90 (1986) 1276-1284] and TraPPE-UA [B. Chen, J.J. Potoff, J.I. Siepmann, Monte Carlo calculations for alcohols and their mixtures with alkanes. Transferable potentials for phase equilibria. Part 5: united-atom description of primary, secondary, and tertiary alcohols, J. Phys. Chem. B 105 (2001) 3093-3104] force fields. Two potentials were compared and TraPPE potential performed better in reproducing densities as a function of pressure, so, it was selected in further structural analysis. The pair distribution functions were obtained and their pressure and temperature dependence were analyzed. In addition, a serial two dimensional distribution functions were plotted to depict the detailed structure of liquid and supercritical ethanol. Based on a widely used geometric criterion, hydrogen bonding statistical results showed that the hydrogen bonds become weaker but still exist under supercritical condition. which are in good agreement with recent experimental measurements. The hydrogen bonds of water, methanol and ethanol were compared and ethanol has nearly the same behavior as methanol under supercritical conditions. (c) 2005 Elsevier B.V. All rights reserved.