Temperature and pressure dependence of the alpha relaxation in ortho- terphenyl

JC Yungbluth and GA Medvedev and BM Savoie and JM Caruthers, JOURNAL OF CHEMICAL PHYSICS, 152, 094504 (2020).

DOI: 10.1063/1.5144283

Molecular dynamics (MD) simulations of ortho-terphenyl using an all-atom model with the optimized potentials for liquid simulations (OPLS) force field were performed both in the high temperature Arrhenian region and at lower temperatures that include the onset of the super-Arrhenian region. From the MD simulations, the internal energy of both the equilibrium liquid and crystal was determined from 300 K to 600 K and at pressures from 0.1 MPa to 1 GPa. The translational and rotational diffusivities were also determined at these temperatures and pressures for the equilibrium liquid. It is shown that within a small offset, the excess internal energy Ux from the MD simulations is consistent with the experimentally determined excess internal energy reported earlier Caruthers and Medvedev, Phys. Rev. Mater. 2, 055604, (2018). The MD mobility data including extremely long-time 1 atm simulations from the study by Eastwood et al. J. Phys. Chem. B 117, 12898, (2013) were combined with experimental data to form a unified dataset, where it was shown that in both the high temperature Arrhenian region and the lower temperature super-Arrhenian region, the mobility is a linear function of 1/Ux(T,p), albeit with different proportionality constants. The transition between the Arrhenian and super-Arrhenian regions is relatively sharp at a critical internal energy Ux alpha. The 1/Ux(T,p) model is able to describe the mobility data over nearly 16 orders-of- magnitude. Other excess thermodynamic properties such as excess enthalpy and excess entropy (i.e., the Adam-Gibbs model) are unable to unify the pressure dependence of the mobility.

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