Dielectric constant and density dependence of the structure of supercritical carbon dioxide using a new modified empirical potential model: a Monte Carlo simulation study.

Two modified versions of the Elementary Physical Model (EPM) [J. Phys. Chem. 1995, 99, 12021] for supercritical carbon dioxide have been proposed in this work and their validities are affirmed by computing the thermodynamic properties and dielectric constant up to 910 kg/m3 with use of canonical ensemble Monte Carlo simulation. Simulations performed for 500 molecules with the EPM2-M model reproduce the experimental data accurately at all thermodynamic states. The structural analyses demonstrate that the aggregation is strong at low density while the coordination number is large at high density. In addition, a detailed study on the radial and angular correlation functions reveals that the T-shaped geometry is dominate while a variety of other structures still appear in the first coordination shell. Furthermore, the angular correlation functions show that the probability of a molecule being oriented toward the convex side of another molecule is equal to that pointing toward the concave side since the molecular nonlinearity of carbon dioxide is only marginal. As the distance between two molecules increases, the preferred orientations disappear quickly and all the results are in good agreement with the prior ab initio calculation [J. Chem. Phys. 2004, 120, 9694].