We investigate by thorough Molecular Dynamics simulations the thermodynamic scaling (TS) of a polymer melt. Two distinct models, with strong and weak virial-energy correlations, are considered. Both evidence the joint TS with the same characteristic exponent γts of the fast mobility -the mean square amplitude of the picosecond rattling motion inside the cage -, and the much slower structural relaxation and chain reorientation. If the cage effect is appreciable, the TS master curves of the fast mobility are nearly linear, grouping in a bundle of approximately concurrent lines for different fragilities. An expression of the TS master curve of the structural relaxation with one adjustable parameter less than the available three-parameters alternatives is derived. The novel expression fits well with the experimental TS master curves of thirty-four glassformers and, in particular, their slope at the glass transition, i.e. the isochoric fragility. For the glassformer OTP the isochoric fragility allows to satisfactorily predict the TS master curve of the fast mobility with no adjustments.

Using molecular dynamics simulations of a molecular liquid, we investigate the thermodynamic scaling (TS) of the structural relaxation time [Formula: see text] in terms of the quantity [Formula: see text], where T and ρ are the temperature and density, respectively. The liquid does not exhibit strong virial-energy correlations. We propose a method for evaluating both the characteristic exponent [Formula: see text] and the TS master curve that uses experimentally accessible quantities that characterise the anharmonic elasticity and does not use details about the microscopic interactions. In particular, we express the TS characteristic exponent [Formula: see text] in terms of the lattice Grüneisen parameter [Formula: see text] and the isochoric anharmonicity [Formula: see text]. An analytic expression of the TS master curve of [Formula: see text] with [Formula: see text] as the key adjustable parameter is found. The comparison with the experimental TS master curves and the isochoric fragilities of 34 glassformers is satisfying. In a few cases, where thermodynamic data are available, we test (i) the predicted characteristic exponent [Formula: see text] and (ii) the isochoric anharmonicity [Formula: see text], as drawn by the best fit of the TS of the structural relaxation, against the available thermodynamic data. A linear relation between the isochoric fragility and the isochoric anharmonicity [Formula: see text] is found and compared favourably with the results of experiments with no adjustable parameters. A relation between the increase of the isochoric vibrational heat capacity due to anharmonicity and the isochoric fragility is derived.