Isomorphs in model molecular liquids.

Isomorphs are curves in the phase diagram along which a number of static and dynamic quantities are invariant in reduced units (Gnan, N.; et al. J. Chem. Phys.2009, 131, 234504). A liquid has good isomorphs if and only if it is strongly correlating, i.e., if the equilibrium virial/potential energy fluctuations are more than 90% correlated in the NVT ensemble. Isomorphs were previously discussed with a focus on atomic systems. This paper generalizes isomorphs to liquids composed of rigid molecules and study the isomorphs of systems of small rigid molecules: the asymmetric dumbbell model, a symmetric inverse power-law dumbbell, and the Lewis-Wahnström o-terphenyl (OTP) model. For all model systems, the following quantities are found to a good approximation to be invariant along an isomorph: the isochoric heat capacity, the excess entropy, the reduced molecular center-of-mass self-part of the intermediate scattering function, and the reduced molecular center-of-mass radial distribution function. In agreement with theory, we also find that an instantaneous change of temperature and density from an equilibrated state point to an isomorphic state point leads to no relaxation. The isomorphs of the Lewis-Wahnström OTP model were found to be more approximative than those of the asymmetric dumbbell model; this is consistent with the OTP model being less strongly correlating. The asymmetric dumbbell and Lewis-Wahnström OTP models each have a "master isomorph"; i.e., the isomorphs have identical shape in the virial/potential energy phase diagram.