Simulation studies of shear viscosity time correlation functions in liquid CS2

The Green—Kubo time correlation function for the shear viscosity in liquid CS2 has been simulated by molecular dynamics at several thermodynamic state points. The breakdown of this function into its kinetic and potential contributions as well as the cross-term between the two has been performed. Intermolecular interactions were obtained from a three-centre atom—atom (12/6) Lennard-Jones potential model. The time correlation functions for the potential part of the shear viscosity contain component two-, three- and four-body terms that were explicitly evaluated to show that they partially cancel each other at short times but at long times, they exhibit approximately exponential decays with magnitude ratios corresponding to nearly perfect cancellation. In this respect, the correlation functions for CS2 resemble those of liquid argon. In addition, the microscopic stress tensor was separated into the portions arising from the repulsive and attractive branches of the Lennard-Jones model. This split gives rise to positive autocorrelation functions involving the repulsive and the attractive forces plus a negative cross-correlation function between the two that partially cancels the contributions of the autocorrelation functions. It is argued that the breakdown of the potential part of the shear viscosity into its component parts is helpful in elucidating the role of molecular re-orientation in determining the separate short and long time behaviours of this time correlation function for liquids such as CS2.