Departures from perfect isomorph behavior in Lennard-Jones fluids and solids

Isomorphs are lines on a fluid or solid phase diagram along which the microstructure is invariant on affine density scaling of the molecular coordinates. Only inverse power (IP) and hard sphere potential systems are perfectly isomorphic. This work provides new theoretical tools and criteria to determine the extent of deviation from perfect isomorphicity for other pair potentials using the Lennard-Jones (LJ) system as a test case. A simple prescription for predicting isomorphs in the fluid range using the freezing line as a reference is shown to be quite accurate for the LJ system. The shear viscosity and self-diffusion coefficient scale well are calculated using this method, which enables comments on the physical significance of the correlations found previously in the literature to be made. The virial-potential energy fluctuation and the concept of an effective IPL system and exponent, n', are investigated, particularly with reference to the LJ freezing and melting lines. It is shown that the exponent, n', converges to the value 12 at a high temperature as similar to T-1/2, where T is the temperature. Analytic expressions are derived for the density, temperature, and radius derivatives of the radial distribution function along an isomorph that can be used in molecular simulation. The variance of the radial distribution function and radial fluctuation function are shown to be isomorph invariant. (c) 2023 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). https://doi.org/10.1063/5.0143651

Automated summary

This work provides new theoretical tools and criteria to determine the extent of deviation from perfect isomorphicity for pair potentials using the Lennard-Jones system as a test case. A simple prediction method using the freezing line as a reference is shown to accurately predict isomorphs in the fluid range for the LJ system. The physical significance of correlations found previously in the literature can be evaluated using this method.