Bulk and shear relaxation in glasses and highly viscous liquids

The ratio between the couplings of a relaxational process to compression and shear, respectively, is calculated in the Eshelby picture of structural rearrangements within a surrounding elastic matrix, assuming a constant density of stable structures in distortion space. The result is compared to experimental data for the low-temperature tunneling states in glasses and to Prigogine-Defay data at the glass transition from the literature.Comment: 6 pages, 2 figures, 53 references; version after understanding the Prigogine-Defay ratio at the glass transition in the accompanying paper arXiv:1203.3555 [cond-mat.dis-nn

Weak links between fast mobility and local structure in molecular and atomic liquids

We investigate by molecular-dynamics simulations, the fast mobility-the rattling amplitude of the particles temporarily trapped by the cage of the neighbors-in mildly supercooled states of dense molecular (linear trimers) and atomic (binary mixtures) liquids. The mixture particles interact by the Lennard-Jones potential. The non-bonded particles of the molecular system are coupled by the more general Mie potential with variable repulsive and attractive exponents in a range which is a characteristic of small n-alkanes and n-alcohols. Possible links between the fast mobility and the geometry of the cage (size and shape) are searched. The correlations on a per-particle basis are rather weak. Instead, if one groups either the particles in fast-mobility subsets or the cages in geometric subsets, the increase of the fast mobility with both the size and the asphericity of the cage is revealed. The observed correlations are weak and differ in states with equal relaxation time. Local forces between a tagged particle and the first-neighbour shell do not correlate with the fast mobility in the molecular liquid. It is concluded that the cage geometry alone is unable to provide a microscopic interpretation of the known, universal link between the fast mobility and the slow structural relaxation. We suggest that the particle fast dynamics is affected by regions beyond the first neighbours, thus supporting the presence of collective, extended fast modes

Universal divergenceless scaling between structural relaxation and caged dynamics in glass-forming systems

On approaching the glass transition, the microscopic kinetic unit spends increasing time rattling in the cage of the first neighbours whereas its average escape time, the structural relaxation time $\tau_\alpha$, increases from a few picoseconds up to thousands of seconds. A thorough study of the correlation between $\tau_\alpha$ and the rattling amplitude, expressed by the Debye-Waller factor (DW), was carried out. Molecular-dynamics (MD) simulations of both a model polymer system and a binary mixture were performed by varying the temperature, the density $\rho$, the potential and the polymer length to consider the structural relaxation as well as both the rotational and the translation diffusion. The simulations evidence the scaling between the $\tau_\alpha$ and the Debye-Waller factor. An analytic model of the master curve is developed in terms of two characteristic length scales pertaining to the distance to be covered by the kinetic unit to reach a transition state. The model does not imply $\tau_\alpha$ divergences. The comparison with the experiments supports the numerical evidence over a range of relaxation times as wide as about eighteen orders of magnitude. A comparison with other scaling and correlation procedures is presented. The study suggests that the equilibrium and the moderately supercooled states of the glassformers possess key information on the huge slowing-down of their relaxation close to the glass transition. The latter, according to the present simulations, exhibits features consistent with the Lindemann melting criterion and the free-volume model.Comment: 8 pages, 11 figure

Feasibility of single-order parameter description of equilibrium viscous liquid dynamics

Molecular dynamics results for the dynamic Prigogine-Defay ratio are presented for two glass-forming liquids, thus evaluating the experimentally relevant quantity for testing whether metastable-equilibrium liquid dynamics to a good approximation are described by a single parameter. For the Kob-Andersen binary Lennard-Jones mixture as well as for an asymmetric dumbbell model liquid a single-parameter description works quite well. This is confirmed by time-domain results where it is found that energy and pressure fluctuations are strongly correlated on the alpha-time scale in the NVT ensemble; in the NpT ensemble energy and volume fluctuations similarly correlate strongly.Comment: Phys. Rev. E, in pres

Time-temperature superposition in viscous liquids

Dielectric relaxation measurements on supercooled triphenyl phosphite show that at low temperatures time-temperature superposition (TTS) is accurately obeyed for the primary (alpha) relaxation process. Measurements on 6 other molecular liquids close to the calorimetric glass transition indicate that TTS is linked to an $\omega^{-1/2}$ high-frequency decay of the alpha loss, while the loss peak width is nonuniversal.Comment: 4 page