USE OF THE MCQUARRIE EQUATION FOR THE COMPUTATION OF SHEAR VISCOSITY VIA EQUILIBRIUM MOLECULAR-DYNAMICS

To date, the calculation of shear viscosity for soft-core fluids via equilibrium molecular dynamics has been done almost exclusively using the Green-Kubo formalism. The alternative mean-squared displacement approach has not been used, except for hard-sphere fluids, in which case the expression proposed by Helfand [Phys. Rev. 119, 1 (1960)] has invariably been selected. When written in the form given by McQuarrie [Statistical Mechanics (Harper & Row, New York, 1976), Chap. 21], however, the mean-squared displacement approach offers significant computational advantages over both its Green-Kubo and Helfand counterparts. In order to achieve comparable statistical significance, the number of experiments needed when using the Green-Kubo or Helfand formalisms is more than an order of magnitude higher than for the McQuarrie expression. For pairwise-additive systems with zero linear momentum, the McQuarrie method yields frame-independent shear viscosities. The hitherto unexplored McQuarrie implementation of the mean-squared displacement approach to shear-viscosity calculation thus appears superior to alternative methods currently in use.