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Understanding the underlying nature of dynamical correlations believed to drive the bulk glass transition is a long-standing problem. Here we show that the form of spatial gradients of the glass transition temperature and structural relaxation time near an interface indeed provide signatures of the nature of relaxation in bulk glass forming liquids. We report results of long-time, large-system molecular dynamics simulations of thick glass-forming polymer films with one vapor interface, supported on a dynamically neutral substrate. We find that gradients in the glass transition temperature and logarithm of the structural relaxation time nucleated at a vapor interface exhibit two distinct regimes: a medium-ranged, large amplitude exponential gradient, followed by a long-range slowly decaying tail that can be described by an inverse power law. This behavior disagrees with multiple proposed theories of glassy dynamics but is predicted by the Elastically Collective Nonlinear Langevin Equation theory as a consequence of two coupled mechanisms: a medium-ranged interface-nucleated gradient of surface modified local caging constraints, and an interfacial truncation of a long-ranged collective elastic field. These findings support a coupled spatially local-nonlocal mechanism of activated glassy relaxation and kinetic vitrification.in both the isotropic bulk and in broken symmetry films. 

Molecular, polymeric, colloidal, and other classes of liquids can exhibit very large, spatially heterogeneous alterations of their dynamics and glass transition temperature when confined to nanoscale domains. Considerable progress has been made in understanding the related problem of near-interface relaxation and diffusion in thick films. However, the origin of “nanoconfinement effects” on the glassy dynamics of thin films, where gradients from different interfaces interact and genuine collective finite size effects may emerge, remains a longstanding open question. Here, we combine molecular dynamics simulations, probing 5 decades of relaxation, and the Elastically Cooperative Nonlinear Langevin Equation (ECNLE) theory, addressing 14 decades in timescale, to establish a microscopic and mechanistic understanding of the key features of altered dynamics in freestanding films spanning the full range from ultrathin to thick films. Simulations and theory are in qualitative and near-quantitative agreement without use of any adjustable parameters. For films of intermediate thickness, the dynamical behavior is well predicted to leading order using a simple linear superposition of thick-film exponential barrier gradients, including a remarkable suppression and flattening of various dynamical gradients in thin films. However, in sufficiently thin films the superposition approximation breaks down due to the emergence of genuine finite size confinement effects. ECNLE theory extended to treat thin films captures the phenomenology found in simulation, without invocation of any critical-like phenomena, on the basis of interface-nucleated gradients of local caging constraints, combined with interfacial and finite size-induced alterations of the collective elastic component of the structural relaxation process.

 

We measured high-quality surface brightness fluctuation (SBF) distances for a sample of 63 massive early-type galaxies using the WFC3/IR camera on the Hubble Space Telescope. The median uncertainty on the SBF distance measurements is 0.085 mag, or 3.9% in distance. Achieving this precision at distances of 50–100 Mpc required significant improvements to the SBF calibration and data analysis procedures for WFC3/IR data. Forty-two of the galaxies are from the MASSIVE Galaxy Survey, a complete sample of massive galaxies within ∼100 Mpc; the SBF distances for these will be used to improve the estimates of the stellar and central supermassive black hole masses in these galaxies. Twenty-four of the galaxies are Type Ia supernova hosts, useful for calibrating SN Ia distances for early-type galaxies and exploring possible systematic trends in the peak luminosities. Our results demonstrate that the SBF method is a powerful and versatile technique for measuring distances to galaxies with evolved stellar populations out to 100 Mpc and constraining the local value of the Hubble constant.