Thermodynamic and kinetic anisotropies in octane thin films

A Haji-Akbari and PG Debenedetti, JOURNAL OF CHEMICAL PHYSICS, 143, 214501 (2015).

DOI: 10.1063/1.4935801

Confinement breaks the translational symmetry of materials, making all thermodynamic and kinetic quantities functions of position. Such symmetry breaking can be used to obtain configurations that are not otherwise accessible in the bulk. Here, we use computer simulations to explore the effect of substrate-liquid interactions on thermodynamic and kinetic anisotropies induced by a solid substrate. We consider n-octane nano-films that are in contact with substrates with varying degrees of attraction, parameterized by an interaction parameter. S. Complete freezing of octane nano-films is observed at low temperatures, irrespective of. S, while at intermediate temperatures, a frozen monolayer emerges at solid-liquid and vapor-liquid interfaces. By carefully inspecting the profiles of translational and orientational relaxation times, we confirm that the translational and orientational degrees of freedom are decoupled at these frozen monolayers. At sufficiently high temperatures, however, free interfaces and solid- liquid interfaces close to loose (low-. S) substrates undergo "pre- freezing," characterized by mild peaks in several thermodynamic quantities. Two distinct dynamic regimes are observed at solid-liquid interfaces. The dynamics is accelerated in the vicinity of loose substrates, while sticky (high-. S) substrates decelerate dynamics, sometimes by as much as two orders of magnitude. These two distinct dynamical regimes have been previously reported by Haji-Akbari and Debenedetti J. Chem. Phys. 141, 024506 (2014) for a model atomic glass-forming liquid. We also confirm the existence of two correlations- proposed in the above-mentioned work-in solid-liquid subsurface regions of octane thin films, i. e., a correlation between atomic density and normal stress, and between atomic translational relaxation time and lateral stress. Finally, we inspect the ability of different regions of an octane film to explore the potential energy landscape by performing inherent structure calculations, and observe no noticeable difference between the free surface and the bulk in efficiently exploring the potential energy landscape. This is unlike the films of model atomic glass formers that tend to sample their respective landscape more efficiently at free surfaces. We discuss the implications of this finding to the ability of octane-and other n-alkanes-to form ultrastable glasses. (C) 2015 AIP Publishing LLC.

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