Models to predict configurational adiabats of Lennard-Jones fluids and their transport coefficients.

Abstract

A comparison is made between three simple approximate formulas for the configurational adiabat (i.e., constant excess entropy, sex) lines in a Lennard-Jones (LJ) fluid, one of which is an analytic formula based on a harmonic approximation, which was derived by Heyes et al. [J. Chem. Phys. 159, 224504 (2023)] (analytic isomorph line, AIL). Another is where the density is normalized by the freezing density at that temperature (freezing isomorph line, FIL). It is found that the AIL formula and the average of the freezing density and the melting density ("FMIL") are configurational adiabats at all densities essentially down to the liquid-vapor binodal. The FIL approximation departs from a configurational adiabat in the vicinity of the liquid-vapor binodal close to the freezing line. The self-diffusion coefficient, D, shear viscosity, ηs, and thermal conductivity, λ, in macroscopic reduced units are essentially constant along the AIL and FMIL at all fluid densities and temperatures, but departures from this trend are found along the FIL at high liquid state densities near the liquid-vapor binodal. This supports growing evidence that for simple model systems with no or few internal degrees of freedom, isodynes are lines of constant excess entropy. It is shown that for the LJ fluid, ηs and D can be predicted accurately by an essentially analytic procedure from the high temperature limiting inverse power fluid values (apart from at very low densities), and this is demonstrated quite well also for the experimental argon viscosity.