Temperature development of glassy alpha-relaxation dynamics determined by broadband dielectric spectroscopy

We present the temperature dependence of alpha-relaxation times of 13 glass formers determined from broadband dielectric spectroscopy, also including data from aging measurements. The data sets partly cover relaxation-time ranges of up to 16 decades enabling a critical test of the validity of model predictions. For this purpose, the data are provided for electronic download. Here we employ these results to test the applicability of the Vogel-Fulcher-Tammann equation and a recently proposed new approach that was demonstrated to provide superior fits of a vast collection of viscosity data.Comment: 6 pages, 5 figures, final version with minor revisions according to referee demands. The relaxation time data published in the present work can be downloaded at http://link.aps.org/supplemental/10.1103/PhysRevE.81.05150

Solidity of Viscous Liquids

Recent NMR experiments on supercooled toluene and glycerol by Hinze and Bohmer show that small rotation angles dominate with only few large molecular rotations. These results are here interpreted by assuming that viscous liquids are solid-like on short length scales. A characteristic length, the "solidity length", separates solid-like behavior from liquid-like behavior.Comment: Plain RevTex file, no figure

Nanometer Scale Dielectric Fluctuations at the Glass Transition

Using non-contact scanning probe microscopy (SPM) techniques, dielectric properties were studied on 50 nanometer length scales in poly-vinyl-acetate (PVAc) films in the vicinity of the glass transition. Low frequency (1/f) noise observed in the measurements, was shown to arise from thermal fluctuations of the electric polarization. Anomalous variations observed in the noise spectrum provide direct evidence for cooperative nano-regions with heterogeneous kinetics. The cooperative length scale was determined. Heterogeneity was long-lived only well below the glass transition for faster than average processes.Comment: 4 pages, 4 embedded PS figures, RevTeX - To appear in Phys. Rev. Let

Metastable liquid-liquid phase transition in a single-component system with only one crystal phase and no density anomaly

We investigate the phase behavior of a single-component system in 3 dimensions with spherically-symmetric, pairwise-additive, soft-core interactions with an attractive well at a long distance, a repulsive soft-core shoulder at an intermediate distance, and a hard-core repulsion at a short distance, similar to potentials used to describe liquid systems such as colloids, protein solutions, or liquid metals. We showed [Nature {\bf 409}, 692 (2001)] that, even with no evidences of the density anomaly, the phase diagram has two first-order fluid-fluid phase transitions, one ending in a gas--low-density liquid (LDL) critical point, and the other in a gas--high-density liquid (HDL) critical point, with a LDL-HDL phase transition at low temperatures. Here we use integral equation calculations to explore the 3-parameter space of the soft-core potential and we perform molecular dynamics simulations in the interesting region of parameters. For the equilibrium phase diagram we analyze the structure of the crystal phase and find that, within the considered range of densities, the structure is independent of the density. Then, we analyze in detail the fluid metastable phases and, by explicit thermodynamic calculation in the supercooled phase, we show the absence of the density anomaly. We suggest that this absence is related to the presence of only one stable crystal structure.Comment: 15 pages, 21 figure

Thermodynamic Behavior of a Model Covalent Material Described by the Environment-Dependent Interatomic Potential

Using molecular dynamics simulations we study the thermodynamic behavior of a single-component covalent material described by the recently proposed Environment-Dependent Interatomic Potential (EDIP). The parameterization of EDIP for silicon exhibits a range of unusual properties typically found in more complex materials, such as the existence of two structurally distinct disordered phases, a density decrease upon melting of the low-temperature amorphous phase, and negative thermal expansion coefficients for both the crystal (at high temperatures) and the amorphous phase (at all temperatures). Structural differences between the two disordered phases also lead to a first-order transition between them, which suggests the existence of a second critical point, as is believed to exist for amorphous forms of frozen water. For EDIP-Si, however, the unusual behavior is associated not only with the open nature of tetrahedral bonding but also with a competition between four-fold (covalent) and five-fold (metallic) coordination. The unusual behavior of the model and its unique ability to simulation the liquid/amorphous transition on molecular-dynamics time scales make it a suitable prototype for fundamental studies of anomalous thermodynamics in disordeered systems.Comment: 48 pages (double-spaced), 13 figure

The Economic Resource Receipt of New Mothers

U.S. federal policies do not provide a universal social safety net of economic support for women during pregnancy or the immediate postpartum period but assume that employment and/or marriage will protect families from poverty. Yet even mothers with considerable human and marital capital may experience disruptions in employment, earnings, and family socioeconomic status postbirth. We use the National Survey of Families and Households to examine the economic resources that mothers with children ages 2 and younger receive postbirth, including employment, spouses, extended family and social network support, and public assistance. Results show that many new mothers receive resources postbirth. Marriage or postbirth employment does not protect new mothers and their families from poverty, but education, race, and the receipt of economic supports from social networks do

Conventional methods fail to measure cp(omega) of glass-forming liquids

The specific heat is frequency dependent in highly viscous liquids. By solving the full one-dimensional thermo-viscoelastic problem analytically it is shown that, because of thermal expansion and the fact that mechanical stresses relax on the same time scale as the enthalpy relaxes, the plane thermal-wave method does not measure the isobaric frequency-dependent specific heat c_p(omega). This method rather measures a "longitudinal" frequency-dependent specific heat, a quantity defined and detailed here that is in-between c_p(omega) and c_v(omega). This result means that no wide-frequency measurements of c_p(omega) on liquids approaching the calorimetric glass transition exist. We briefly discuss consequences for experiment

Proton Spin-Lattice Relaxation in Organic Molecular Solids: Polymorphism and the Dependence on Sample Preparation

We report solid‐state nuclear magnetic resonance 1H spin‐lattice relaxation, single‐crystal X‐ray diffraction, powder X‐ray diffraction, field emission scanning electron microscopy, and differential scanning calorimetry in solid samples of 2‐ethylanthracene (EA) and 2‐ethylanthraquinone (EAQ) that have been physically purified in different ways from the same commercial starting compounds. The solid‐state 1H spin‐lattice relaxation is always non‐exponential at high temperatures as expected when CH3 rotation is responsible for the relaxation. The 1H spin‐lattice relaxation experiments are very sensitive to the “several‐molecule” (clusters) structure of these van der Waals molecular solids. In the three differently prepared samples of EAQ, the relaxation also becomes very non‐exponential at low temperatures. This is very unusual and the decay of the nuclear magnetization can be fitted with both a stretched exponential and a double exponential. This unusual result correlates with the powder X‐ray diffractometry results and suggests that the anomalous relaxation is due to crystallites of two (or more) different polymorphs (concomitant polymorphism)