Scaling Properties of Liquid Dynamics Predicted from a Single Configuration: Pseudoisomorphs for Harmonic-Bonded Molecules

Abstract

Isomorphs are curves in the thermodynamic phase diagram of invariant excess entropy, structure, and dynamics, while pseudoisomorphs are curves of invariant structure and dynamics, but not of the excess entropy. The latter curves have been shown to exist in molecular models with flexible bonds [OlsenA. E. Olsen, A. E. 241103J. Chem. Phys.2016145]. We here present three force-based methods to trace out pseudoisomorphs based on a single configuration and test them on the asymmetric dumbbell and 10-bead Lennard-Jones chain models with bonds modeled as harmonic springs. The three methods are based on requiring that particle forces, center-of-mass forces, and torques, respectively, are invariant in reduced units. For each of the two investigated models we identify a method that works well for tracing out pseudoisomorphs, but these methods are not the same. Overall, we find that the more internal degrees of freedom there are in the molecule studied, the less they appear to affect the gross dynamical behavior. Moreover, the “internal” degrees of freedom (including rotation) do not significantly affect the scaling behavior of the dynamical/transport coefficients provided some ’quenching’ is performed.