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Glass films prepared by a process of physical vapor deposition have been shown to have thermodynamic and kinetic stability comparable to those of ordinary glasses aged for thousands of years. A central question in the study of vapor-deposited glasses, particularly in light of new knowledge regarding anisotropy in these materials, is whether the ultra-stable glassy films formed by vapor deposition are ever equivalent to those obtained by liquid cooling. We present a computational study of vapor deposition for a two-dimensional glass forming liquid using a methodology which closely mimics experiment. We find that for the model considered here, structures that arise in vapor-deposited materials are statistically identical to those observed in ordinary glasses, provided the two are compared at the same inherent structure energy. We also find that newly deposited hot molecules produce cascades of hot particles that propagate far into the film, possibly influencing the relaxation of the material.

Glasses produced via physical vapor deposition can display greater kinetic stability and lower enthalpy than glasses prepared by liquid cooling. While the reduced enthalpy has often been used as a measure of the stability, it is not obvious whether dynamic measures of stability provide the same view. Here, we study dynamics in vapor-deposited and liquid-cooled glass films using molecular simulations of a bead-spring polymer model as well as a Lennard-Jones binary mixture in two and three dimensions. We confirm that the dynamics in vapor-deposited glasses is indeed slower than in ordinary glasses. We further show that the inherent structure energy is a good reporter of local dynamics, and that aged systems and glasses prepared by cooling at progressively slower rates exhibit the same behavior as vapor-deposited materials when they both have the same inherent structure energy. These findings suggest that the stability inferred from measurements of the energy is also manifested in dynamic observables, and they strengthen the view that vapor deposition processes provide an effective strategy for creation of stable glasses., Comment: 10 pages, 8 figures, to be submitted to Soft Matter

A growing body of experimental work indicates that physical vapor deposition provides an effective route for preparation of stable glasses, whose properties correspond in some cases to those expected for glasses that have been aged for thousands of years. In this work, model binary glasses are prepared in a process inspired by physical vapor deposition, in which particles are sequentially added to the free surface of a growing film. The resulting glasses are shown to be more stable than those prepared by gradual cooling from the liquid phase. However, it is also shown that the composition of the resulting glass, which is difficult to control in physical vapor deposition simulations of thin films, plays a significant role on the physical characteristics of the material. That composition dependence leads to a re- evaluation of previous results from simulations of thinner films than those considered here, where the equivalent age of the corresponding glasses was overestimated. The simulations presented in this work, which correspond to films that are approximately 38 molecular diameters thick, also enable analysis of the devitrification mechanism of vapor-deposited glasses. Consistent with experiments, it is found that this mechanism consists of a mobility front that propagates from the free interface into the interior of the films. Eliminating surface mobility eliminates this route of transformation into the supercooled liquid., Comment: 11 pages, 6 figures. Submitted to J.Chem.Phys

Numerically optimized reduced descriptions of macromolecular liquids often present thermodynamic inconsistency with atomistic level descriptions even if the total correlation function, i.e. the structure, appears to be in agreement. An analytical expression for the effective potential between a pair of coarse-grained units is derived starting from the first-principles Ornstein-Zernike equation, for a polymer liquid where each chain is represented as a collection of interpenetrating blobs, with a variable number of blobs, $n_b$, of size $N_b$. The potential is characterized by a long tail, slowly decaying with characteristic scaling exponent of $N_b^{1/4}$. This general result applies to any coarse-grained model of polymer melts with units larger than the persistence length, highlighting the importance of the long, repulsive, potential tail for the model to correctly predict both structural and thermodynamic properties of the macromolecular liquid.