title: Pressure-energy correlations in liquids. IV. "Isomorphs" in liquid phase diagrams.
abstract: This paper is the fourth in a series devoted to identifying and explaining the properties of strongly correlating liquids, i.e., liquids where virial and potential energy correlate better than 90% in their thermal equilibrium fluctuations in the NVT ensemble. For such liquids we here introduce the concept of "isomorphic" curves in the phase diagram. A number of thermodynamic, static, and dynamic isomorph invariants are identified. These include the excess entropy, the isochoric specific heat, reduced-unit static and dynamic correlation functions, as well as reduced-unit transport coefficients. The dynamic invariants apply for both Newtonian and Brownian dynamics. It is shown that after a jump between isomorphic state points the system is instantaneously in thermal equilibrium; consequences of this for generic aging experiments are discussed. Selected isomorph predictions are validated by computer simulations of the Kob-Andersen binary Lennard-Jones mixture, which is a strongly correlating liquid. The final section of the paper relates the isomorph concept to phenomenological melting rules, Rosenfeld's excess entropy scaling, Young and Andersen's approximate scaling principle, and the two-order parameter maps of Debenedetti and co-workers. This section also shows how the existence of isomorphs implies an "isomorph filter" for theories for the non-Arrhenius temperature dependence of viscous liquids' relaxation time, and it explains isochronal superposition for strongly correlating viscous liquids.
authors.affiliation: DNRF Center Glass and Time, IMFUFA, Department of Sciences, Roskilde University, P.O. Box 260, DK-4000 Roskilde, Denmark. ngnan@ruc.dk
authors.forename: Nicoletta
authors.initials: N
authors.lastname: Gnan
authors.forename: Thomas B
authors.initials: TB
authors.lastname: Schrøder
authors.forename: Ulf R
authors.initials: UR
authors.lastname: Pedersen
authors.forename: Nicholas P
authors.initials: NP
authors.lastname: Bailey
authors.forename: Jeppe C
authors.initials: JC
authors.lastname: Dyre