The relaxation dynamics of a confined glassy simple liquid

We use molecular-dynamics computer simulations to study the relaxation dynamics of a confined simple liquid. Two types of confining walls are considered: A rough wall and a smooth wall. The simulation is set up in such a way that the static properties of the confined system are identical to the ones of the bulk. Nevertheless, we find that upon cooling the relaxation dynamics of the confined systems differ strongly from the one of the bulk. In particular, we find that close to the rough/smooth wall this dynamics is slowed down/accelerated by orders of magnitude. Using these results we are able to extract a dynamical length scale of the system and we show that this length shows an Arrhenius dependence.Received: 1 January 2003, Published online: 14 October 2003PACS: 64.70.Pf Glass transitions - 68.15. + e Liquid thin films - 02.70.Ns Molecular dynamics and particle methods     

Crystallisation and molecular mobilities in liquid and glassy states of a MXD6 polyamide

The dynamic of molecular mobilities occurring above and below the glass transition of a polyamide called MXD6 have been investigated on samples with different degrees of crystallinity. The fragility index (m) has been evaluated for a fully amorphous material and it was found that m = 180 classifies this material as fragile in regard to the strong-fragile glass forming liquid concept. For semi-crystalline samples, the results show two relaxation processes at the glass transition. One can be attributed to the molecular mobility existing in the free amorphous domain, and the second peak to a molecular mobility existing in a rigid amorphous domain as proposed by the '3-phase model'. The existence of these two phenomena does not allow a correct determination of the fragility index for such semi-crystalline materials by means of calorimetric investigation.     

Acoustic dissipation and density of states in liquid, supercooled, and glassy glycerol

Combined Brillouin spectra collected at visible, ultraviolet, and x-ray frequencies are used to reconstruct the imaginary part of the acoustic compliance J' over a wide frequency range between 0.5 GHz and 5 THz. For liquid, supercooled, and glassy glycerol, J' is found to be linearly dependent on the tagged-particle susceptibility measured by incoherent neutron scattering up to ?1 THz, giving evidence of a clear relation between acoustic power dissipation and density of states. A simple but general formalism is presented to quantitatively explain this relation, thus clarifying the connection between the quasielastic component observed in neutron scattering experiments and the fast relaxation dynamics probed by Brillouin scattering.     

Vibrational states of glassy and crystalline orthoterphenyl

Low-frequency vibrations of glassy and crystalline orthoterphenyl are studied by means of neutron scattering. Phonon dispersions are measured along the main axes of a single crystal, and the corresponding longitudinal and transversal sound velocities are obtained. For glassy and polycrystalline samples, a density of vibrational states is determined and cross-checked against other dynamic observables. In the crystal, low-lying zone-boundary modes lead to an excess over the Debye density of states. In the glass, the boson peak is located at even lower frequencies. With increasing temperature, both glass and crystal show anharmonicity. Received 7 December 1999     

Preparation of cluster states with trapped electrons on a liquid helium surface

We present a scheme for the preparation of one-dimensional (1D) and two-dimensional (2D) cluster states with electrons trapped on a liquid helium surface and driven by a classical laser beam. The two lowest levels of the vertical motion of the electron act as a two-level system, and the quantized vibration of the electron along one of the parallel directions (the x direction) serves as the bosonic mode. The degrees of freedom of the vertical and parallel motions of the trapped electron can be coupled together by a classical laser field. With the proper frequency of the laser field, the cluster states can be realized.     

Measuring surface and bulk relaxation in glassy polymers

We present a comprehensive study of gold nanoparticle embedding into polystyrene (PS) surfaces at temperatures ranging from T _g + 8 K to T _g − 83 K and times as long as 10⁵ minutes. This range in times and temperatures allows the first concurrent observation of and differentiation between surface and bulk behavior in the 20nm region nearest the free surface of the polymer film. Of particular importance is the temperature region near the bulk glass transition temperature where both surface and bulk processes can be measured. The results indicate that for the case of PS, enhanced surface mobility only exists at temperatures near or below the bulk T _g value. The surface relaxation times are only weakly temperature dependent and near T _g , the enhanced mobility extends less than 10nm into the bulk of the film. The results suggest that both the concept of a “surface glass transition” and the use of glass transition temperatures to measure local mobility near interfaces may not universally apply to all polymers. The results can also be used to make a quantitative connection to molecular dynamics simulations of polymer films and surfaces.     

Study of fast relaxation in a glassy polymer by far-IR spectroscopy

The temperature dependence of the far-IR spectra of glassy polymethylmethacrylate is studied in the range of ν = 10–130 cm^–1 at temperatures from 90 to 420 K. The analysis of the spectra revealed absorption corresponding to two rapid relaxation processes: (1) 180°-rotation of the OCO plane of the side groups and (2) reorientation of the links of the main chain. The activation energies of these processes are determined.

     

Dielectric relaxation and AC conduction of an AgTlSe2 semiconductor in the solid and liquid states

Measurements of the dielectric properties of AgTlSe₂ in the solid and liquid states were carried out in a wide range of frequencies and temperatures. The material displayed dielectric dispersion, and a loss peak was observed. Cole-Cole diagrams have been used to determine the distribution parameter (a) and the molecular relaxation time (). The process of dielectric relaxation (loss) and ac conduction was attributed to the correlated barrier hopping model suggested by Elliott for amorphous solids, where two carriers simultaneously hop over a barrier between charged defectD ⁺ andD ^– states.     

Correlations in binary liquid and glassy metals

It is shown, starting from a nearly-free electron approximation, how correlations can occur in the atomic positions of binary liquid and glassy alloys. In particular, it follows from energy considerations that for an alloy of a transition metal with a metalloid there is a concentration region where there should be no metalloid-metalloid nearest neighbors. This concentration region is just the same as that where glass formation is often observed in these systems.     

On relaxation of entangled states in a collective thermostat

A kinetic equation describing collective relaxation process in the dispersion limit is derived for an ensemble of two-level atoms placed in a cavity and interacting with one cavity mode. Multiatom entangled states belonging to the set of Dicke states and insensitive to collective decay are found. A scheme for recording, storing, and reading these states with participation of spatially multimode light is reported.     

Dynamic model of super-arrhenius relaxation rates in glassy materials

Super-Arrhenius relaxation rates in glassy materials can be associated with thermally activated rearrangements of increasing numbers of molecules at decreasing temperatures. We explore a model of such a mechanism in which stringlike fluctuations in the neighborhood of shear transformation zones provide routes along which rearrangements can propagate, and the entropy associated with critically long strings allows the rearrangement to be distributed stably in the surrounding material. We further postulate that, at low enough temperatures, these fluctuations are localized on the interfaces between frustration-limited domains, and in this way obtain a modified Vogel-Fulcher formula for the relaxation rate.     

Electrical resistivity of ternary glassy and liquid Pd-alloys

The electrical resistivity of liquid (Pd₁₀₀Cu_100?x)₈₀Ge₂₀ alloys has been measured as a function of temperature. For Cu-rich negative temperature coefficients and for Pd-rich alloys positive temperature coefficients of the electrical resistivity have been observed. This behavior is very similar to recent observed resistivity temperature curves of glassy (Pd₁₀₀Cu_100?x)₈₀P₂₀ alloys. An explanation of the resistivity behavior in terms of liquid metals theory is suggested.     

Evolution operator and stable coherent states

The time evolution of a coherent state is discussed using the evolution operator of the underlying Hamiltonian.     

Time-dependent invariants and stable coherent states

The time evolution of a coherent state is discussed using an explicitly time-dependent invariant of the underlying hamiltonian. It is shown that a stable coherent state is an eigenstate of such an invariant.     

Structural relaxation investigations of glassy polystyrene by radial distribution functions

The structural relaxation of an atactic polystyrene under sub-T _g annealing at 50°C and at 70°C was investigated by the radial distribution function (RDF) derived from its wide-angle x-ray scattering (WAXS). By recording the changes in RDF (i.e., ΔH(r), where r is the radial distance from an arbitrary reference atom) after it had been annealed for a certain period of days, and taking the integration of ΔAH(r) ²dr, we found that the atom density within structural domains in a size below 15 Å was changed dramatically, but that the tendency leveled off as annealing proceeded. However, the atom density outside the domains is barely changed by sub-T _g annealing. The size of the domain is similar to the statistical segment length reported in the literature. The behavior of the domains—that the segmental relaxation inside the domains in the initial sub-T _g annealing is unconstrained by their neighbors outside the domains—is also similar to the behavior of the statistical segments. The domains are believed to be composed of a statistical segment across the center, which has about 6 styrene repeat units, and 6 equal-distanced parallel segments tangent to the edge of the domain. On the other hand, as the annealing temperature is closer to the glass transition temperature, the frozen unstable chain segments reach equilibrium sooner and with less disturbance in their conformation.     

The entropy difference between the Lennard-Jones crystalline and glassy states

Entropy changes of isochoric Lennard-Jones fluid-crystal and fluid-glass transitions, calculated by molecular dynamics and integration of $\text{d}\text{S =}\text{d}\text{Q}\text{T}$, are approximately equal. The entropy difference between crystal and glass, at the same density and temperature, is thus negligibly small.