Stable glasses are formed during physical vapor deposition (PVD), through the surface-mediated equilibration process. Understanding surface relaxation dynamics is important in understanding the details of this process. Direct measurements of the surface relaxation times in molecular glass systems are challenging. As such, surface diffusion measurements have been used in the past as a proxy for the surface relaxation process. In this study, we show that the absence of enhanced surface diffusion is not a reliable predictor of reduced ability to produce stable glasses. To demonstrate, we have prepared stable glasses (SGs) from two structurally similar organic molecules, 1,3-bis­(1-naphthyl)-5-(2-naphthyl)­benzene (TNB) and 9-(3,5-di­(naphthalen-1-yl)­phenyl)­anthracene (α,α-A), with similar density increase and improved kinetic stability as compared to their liquid-quenched (LQ) counterparts. The surface diffusion values of these glasses were measured both in the LQ and SG states below their glass transition temperatures (T gs) using gold nanorod probes. While TNB shows enhanced surface diffusion in both SG and LQ states, no significant surface T g diffusion is observed on the surface of α,α-A within our experimental time scales. However, isothermal dewetting experiments on ultrathin films of both molecules below Tg indicate the existence of enhanced dynamics in ultrathin films for both molecules, indirectly showing the existence of an enhanced mobile surface layer. Both films produce stable glasses, which is another indication for the existence of the mobile surface layer. Our results suggest that lateral surface diffusion may not be a good proxy for enhanced surface relaxation dynamics required to produce stable glasses, and thus, other types of measurements to directly probe the surface relaxation times may be necessary.

Stable glasses (SGs) are formed through surface-mediated equilibration (SME) during physical vapor deposition (PVD). Unlike intermolecular interactions, the role of intramolecular degrees of freedom in this process remain unexplored. Here, using experiments and coarse-grained molecular dynamics simulations, we demonstrate that varying dihedral rotation barriers of even a single bond, in otherwise isomeric molecules, can strongly influence the structure and stability of PVD glasses. These effects arise from variations in the degree of surface mobility, mobility gradients, and mobility anisotropy, at a given deposition temperature (Tdep) At high Tdep, flexible molecules have access to more configurations, which enhances the rate of SME, forming isotropic SGs. At low Tdep, stability is achieved by out of equilibrium aging of the surface layer. Here, the poor packing of rigid molecules enhances the rate of surface-mediated aging (SMA), producing stable glasses with layered structures in a broad range of Tdep. In contrast, the dynamics of flexible molecules couple more efficiently to the glass layers underneath, resulting in reduced mobility and weaker mobility gradients, producing unstable glasses. Independent of stability, the flattened shape of flexible molecules can also promote in-plane orientation orderat low Tdep. These results indicate that small changes in intramolecular relaxation barriers can be used as an approach to independently tune the structure and mobility profiles of the surface layer and thus the stability and structure of PVD glasses.

Glasses formed by physical vapor deposition (PVD) are an interesting new class of materials, exhibiting properties thought to be equivalent to those of glasses aged for thousands of years. Exerting control over the structure and properties of PVD glasses formed with different types of glass-forming molecules is now an emerging challenge. In this work, we study coarse grained models of organic glass formers containing fluorocarbon tails of increasing length, corresponding to an increased tendency to form microstructures. We use simulated PVD to examine how the presence of the microphase separated domains in the supercooled liquid influences the ability to form stable glasses. This model suggests that increasing molecule tail length results in decreased thermodynamic and kinetic stability of the molecules in PVD films. The reduced stability is further linked to the reduced ability of these molecules to equilibrate at the free surface during PVD. We find that as the tail length is increased, the relaxation time near the surface of the supercooled equilibrium liquid films of these molecules are slowed and become essentially bulk-like, due to the segregation of the fluorocarbon tails to the free surface. Surface diffusion is also markedly reduced due to clustering of the molecules at the surface. Based on these results, we propose a trapping mechanism where tails are unable to move between local phase separated domains on the relevant deposition time scales.

When aged below the glass transition temperature, Tg, the density of a glass cannot exceed that of the metastable supercooled liquid (SCL) state, unless crystals are nucleated. The only exception is when another polyamorphic SCL state exists, with a density higher than that of the ordinary SCL. Experimentally, such polyamorphic states and their corresponding liquid–liquid phase transitions have only been observed in network-forming systems or those with polymorphic crystalline states. In otherwise simple liquids, such phase transitions have not been observed, either in aged or vapor-deposited stable glasses, even near the Kauzmann temperature. Here, we report that the density of thin vapor-deposited films of N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD) can exceed their corresponding SCL density by as much as 3.5% and can even exceed the crystal density under certain deposition conditions. We identify a previously unidentified high-density supercooled liquid (HD-SCL) phase with a liquid–liquid phase transition temperature (TLL) ∼35 K below the nominal glass transition temperature of the ordinary SCL. The HD-SCL state is observed in glasses deposited in the thickness range of 25 to 55 nm, where thin films of the ordinary SCL have exceptionally enhanced surface mobility with large mobility gradients. The enhanced mobility enables vapor-deposited thin films to overcome kinetic barriers for relaxation and access the HD-SCL state. The HD-SCL state is only thermodynamically favored in thin films and transforms rapidly to the ordinary SCL when the vapor deposition is continued to form films with thicknesses more than 60 nm.

The torsional ground state for ethane, the torsional, rotational, and mixed torsional and rotational ground state of propane are computed with a version of diffusion Monte Carlo adapted to handle the geometric complexity of curved spaces such as the Ramachandra space. The quantum NVT ensemble average for the mixed torsional and rotational degrees of freedom of propane is computed, using a version of Monte Carlo path integral, also adapted to handle curved spaces. These three problems are selected to demonstrate the generality and the applicability of the approaches described. The spaces of coordinates can be best constructed from the parameters of continuous Lie groups, and alternative methods based on vector spaces, where extended Lagrangian terms would be too cumbersome to implement. We note that the geometric coupling between the torsions and the rotations of propane produces a substantial effect on the ground state energy of propane, and that the quantum effects on the energy of propane are quite large even well above room temperature.