What constitutes a simple liquid?

TL;DR

This paper proposes redefining simple liquids based on strong virial-potential energy correlation, emphasizing the importance of the first coordination shell and challenging traditional views on intermolecular forces.

Contribution

It introduces a new definition of simple liquids based on fluctuation correlations and demonstrates its validity through NVT simulations of various model liquids.

Findings

Strong virial-potential energy correlation indicates interactions can be limited to the first coordination shell.

Not all atomic liquids are simple, and not all simple liquids are atomic.

The FCS-based definition questions traditional perturbation theory assumptions.

Abstract

Simple liquids are traditionally defined as many-body systems of classical particles interacting via radially symmetric pair potentials. We suggest that a simple liquid should be defined instead by the property of having strong correlation between virial and potential energy equilibrium fluctuations in the NVT ensemble. There is considerable overlap between the two definitions, but also some notable differences. For instance, in the new definition simplicity is not a property of the intermolecular potential only because a liquid is usually only strongly correlating in part of its phase diagram. Moreover, according to the new definition not all simple liquids are atomic (i.e., with radially symmetric pair potentials) and not all atomic liquids are simple. The main part of the paper motivates the new definition of liquid simplicity by presenting evidence that a liquid is strongly correlating if and only if its intermolecular interactions may be ignored beyond the first coordination shell (FCS). This is demonstrated by NVT simulations of structure and dynamics of 15 atomic and molecular model liquids with a shifted-forces cutoff placed at the first minimum of the radial distribution function. No proof is given that the chemical characterization follows from the strong correlation property, but it is shown to be consistent with the existence of isomorphs in strongly correlating liquids' phase diagram. Finally, we note that the FCS characterization of simple liquids calls into question the basis for standard perturbation theory, according to which the repulsive and attractive forces play fundamentally different roles for the physics of liquids.