PNNL

Abstract

A series of molecular dynamics simulations were carried out to examine the thermodynamic and the structural properties of the liquid and liquid/vapor of chloroform. A polarizable potential model was used to describe the intermolecular chloroform-chloroform interactions. The computed liquid densities and the enthalpies of vaporization and their corresponding temperature dependence are in excellent agreement with experimental values. The radial distribution functions and the corresponding neutron scattering cross sections were critically evaluated against the experimental data. The agreement between both approaches was found to be quite reasonable. The equilibrium interfacial properties of the chloroform liquid/vapor were also evaluated. The computed density profile shows that the interface is not sharp at a microscopic level and has a thickness of 5.9 Å at 298 K. The calculated surface tensions as a function of temperature are in good agreement with the corresponding experimental data. Accurate ab initio calculations were also carried out on the chloroform dimer, and the result for the binding energy was in good agreement with the value obtained from the molecular dynamics model.