Virial-potential-energy correlation and its relation to density scaling for quasireal model systems.

In this paper, we examine the virial- and the potential-energy correlation for quasireal model systems. This correlation constitutes the framework of the theory of the isomorph in the liquid phase diagram commonly examined using simple liquids. Interestingly, our results show that for the systems characterized by structural anisotropy and flexible bonds, the instantaneous values of total virial and total potential energy are entirely uncorrelated. It is due to the presence of the intramolecular interactions because the contributions to the virial and potential energy resulting from the intermolecular interactions still exhibit strong linear dependence. Interestingly, in contrast to the results reported for simple liquids, the slope of the mentioned linear dependence is different than the values of the density scaling exponent. However, our findings show that for quasireal materials, the slope of dependence between the virial and potential energy (resulting from the intermolecular interactions) strongly depends on the interval of intermolecular distances that are taken into account. Consequently, the value of the slope of the discussed relationship, which enables satisfactory density scaling, can be obtained. Interestingly, this conclusion is supported by the results obtained for analogous systems without intermolecular attraction, for which the value the slope of the virial-potential-energy correlation is independent of considered intermolecular distances, directly corresponds to the exponent of the intermolecular repulsion, and finally leads to accurate density scaling.