A Novel Route to Calculate the Length Scale for the Glass Transition in Polymers

The occurrence of glass transition is believed to be associated to cooperative motion with a growing length scale with decreasing temperature. We provide a novel route to calculate the size of cooperatively rearranging regions CRR of glass-forming polymers combining the Adam-Gibbs theory of the glass transition with the self-concentration concept. To do so we explore the dynamics of glass-forming polymers in different environments. The material specific parameter $\alpha$ connecting the size of the CRR to the configurational entropy is obtained in this way. Thereby, the size of CRR can be precisely quantified in absolute values. This size results to be in the range 1 $\div$ 3 nm at the glass transition temperature depending on the glass-forming polymer

Relaxation Scenarios in a Mixture of Large and Small Spheres: Dependence on the Size Disparity

We present a computational investigation on the slow dynamics of a mixture of large and small soft spheres. By varying the size disparity at a moderate fixed composition different relaxation scenarios are observed for the small particles. For small disparity density-density correlators exhibit moderate stretching. Only small quantitative differences are observed between dynamic features for large and small particles. On the contrary, large disparity induces a clear time scale separation between the large and the small particles. Density-density correlators for the small particles become extremely stretched, and display logarithmic relaxation by properly tuning the temperature or the wavevector. Self-correlators decay much faster than density-density correlators. For very large size disparity, a complete separation between self- and collective dynamics is observed for the small particles. Self-correlators decay to zero at temperatures where density-density correlations are frozen. The dynamic picture obtained by varying the size disparity resembles features associated to Mode Coupling transition lines of the types B and A at, respectively, small and very large size disparity. Both lines might merge, at some intermediate disparity, at a higher-order point, to which logarithmic relaxation would be associated. This picture resembles predictions of a recent Mode Coupling Theory for fluids confined in matrixes with interconnected voids [V. Krakoviack, Phys. Rev. Lett. {\bf 94}, 065703 (2005)].Comment: Journal of Chemical Physics 125, 164507 (2006

Tests of mode coupling theory in a simple model for two-component miscible polymer blends

We present molecular dynamics simulations on the structural relaxation of a simple bead-spring model for polymer blends. The introduction of a different monomer size induces a large time scale separation for the dynamics of the two components. Simulation results for a large set of observables probing density correlations, Rouse modes, and orientations of bond and chain end-to-end vectors, are analyzed within the framework of the Mode Coupling Theory (MCT). An unusually large value of the exponent parameter is obtained. This feature suggests the possibility of an underlying higher-order MCT scenario for dynamic arrest.Comment: Revised version. Additional figures and citation

Anomalous Dynamic Arrest in a Mixture of Big and Small Particles

We present molecular dynamics simulations on the slow dynamics of a mixture of big and small soft-spheres with a large size disparity. Dynamics are investigated in a broad range of temperature and mixture composition. As a consequence of large size disparity, big and small particles exhibit very different relaxation times. As previously reported for simple models of short-ranged attractive colloids and polymer blends, several anomalous dynamic features are observed: i) sublinear behavior for mean squared displacements, ii) concave-to-convex crossover for density-density correlators, by varying temperature or wavevector, iii) logarithmic decay for specific wavevectors of density-density correlators. These anomalous features are observed over time intervals extending up to four decades, and strongly resemble predictions of the Mode Coupling Theory (MCT) for state points close to higher-order MCT transitions, which originate from the competition between different mechanisms for dynamic arrest. For the big particles we suggest competition between soft-sphere repulsion and depletion effects induced by neighboring small particles. For the small particles we suggest competition between bulk-like dynamics and confinement, respectively induced by neighboring small particles and by the slow matrix of big particles. By increasing the size disparity, a new relaxation scenario arises for the small particles. Self-correlators decay to zero at temperatures where density-density correlations are frozen. The behavior of the latters resembles features characteristic of type-A MCT transitions, defined by a zero value of the critical non-ergodicity parameter.Comment: Version 2. Added major new result

Methyl group dynamics in a confined glass

We present a neutron scattering investigation on methyl group dynamics in glassy toluene confined in mesoporous silicates of different pore sizes. The experimental results have been analysed in terms of a barrier distribution model, such a distribution following from the structural disorder in the glassy state. Confinement results in a strong decreasing of the average rotational barrier in comparison to the bulk state. We have roughly separated the distribution for the confined state in a bulk-like and a surface-like contribution, corresponding to rotors at a distance from the pore wall respectively larger and smaller than the spatial range of the interactions which contribute to the rotational potential for the methyl groups. We have estimated a distance of 7 Amstrong as a lower limit of the interaction range, beyond the typical nearest-neighbour distance between centers-of-mass (4.7 Amstrong).Comment: 5 pages, 3 figures. To be published in European Physical Journal E Direct. Proceedings of the 2nd International Workshop on Dynamics in Confinemen

X-ray Spectra of the RIXOS source sample

We present results of an extensive study of the X-ray spectral properties of sources detected in the RIXOS survey, that is nearly complete down to a flux limit of 3e-14 cgs (0.5-2 keV). We show that for X-ray surveys containing sources with low count rate spectral slopes estimated using simple hardness ratios in the ROSAT band can be biased. Instead we analyse three-colour X-ray data using statistical techniques appropriate to the Poisson regime which removes the effects of this bias. We have then applied this technique to the RIXOS survey to study the spectral properties of the sample. For the AGN we find an average energy index of 1.05+-0.05 with no evidence for spectral evolution with redshift. Individual AGN are shown to have a range of properties including soft X-ray excesses and intrinsic absorption. Narrow Emission Line Galaxies also seem to fit to a power-law spectrum, which may indicate a non-thermal origin for their X-ray emission. We infer that most of the clusters in the sample have a bremsstrahlung temperature >3 keV, although some show evidence for a cooling flow. The stars deviate strongly from a power-law model but fit to a thermal model. Finally, we have analysed the whole RIXOS sample containing 1762 sources. We find that the mean spectral slope of the sources hardens at lower fluxes in agreement with results from other samples. However, a study of the individual sources demonstrates that the hardening of the mean is caused by the appearance of a population of very hard sources at the lowest fluxes. This has implications for the nature of the soft X-ray background.Comment: 31,LaTeX file, 2 PS files with Table 2 and 22 PS figures. MNRAS in pres

Chandra Multiwavelength Project: Normal Galaxies at Intermediate Redshift

(abridged) We have investigated 136 Chandra extragalactic sources without broad optical emission lines, including 93 galaxies with narrow emission lines (NELG) and 43 with only absorption lines (ALG). Based on fx/fo, Lx, X-ray spectral hardness and optical emission line diagnostics, we have conservatively classified 36 normal galaxies (20 spirals and 16 ellipticals) and 71 AGNs. We found no statistically significant evolution in Lx/LB, within the limited z range. We have built log(N)-log(S), after correcting for completeness based on a series of simulations. The best-fit slope is -1.5 for both S and B energy bands, which is considerably steeper than that of the AGN-dominated cosmic background sources, but slightly flatter than the previous estimate, indicating normal galaxies will not exceed the AGN population until fx ~ 2 x 10-18 erg s-1 cm-2 (a factor of ~5 lower than the previous estimate). A group of NELGs appear to be heavily obscured in X-rays, i.e., a typical type 2 AGN. After correcting for intrinsic absorption, their X-ray luminosities could be Lx > 10^44 erg s-1, making them type 2 quasar candidates. While most X-ray luminous ALGs (XBONG - X-ray bright, optically normal galaxy candidates) do not appear to be significantly absorbed, we found two heavily obscured objects, which could be as luminous as an unobscured broad-line quasar. Among 43 ALGs, we found two E+A galaxy candidates with strong Balmer absorption lines, but no [OII] line. The X-ray spectra of both galaxies are soft and one of them has a nearby close companion galaxy, supporting the merger/interaction scenario rather than the dusty starburst hypothesis.Comment: 31 pages, 9 figures, accepted for publication in ApJ (20 June 2006, v644), replaced with minor correction

Glassy Dynamics of Protein Folding

A coarse grained model of a random polypeptide chain, with only discrete torsional degrees of freedom and Hookean springs connecting pairs of hydrophobic residues is shown to display stretched exponential relaxation under Metropolis dynamics at low temperatures with the exponent $\beta\simeq 1/4$, in agreement with the best experimental results. The time dependent correlation functions for fluctuations about the native state, computed in the Gaussian approximation for real proteins, have also been found to have the same functional form. Our results indicate that the energy landscape exhibits universal features over a very large range of energies and is relatively independent of the specific dynamics.Comment: RevTeX, 4 pages, multicolumn, including 5 figures; larger computations performed, error bars improve

Self- and Collective Dynamics of Syndiotactic Poly(methylmethacrylate). A Combined Study by Quasielastic Neutron Scattering and Atomistic Molecular Dynamics Simulations

We have investigated the molecular dynamics of syndiotactic poly(methyl methacrylate) well above the glass transition by combining quasielastic neutron scattering and fully atomistic computer simulations. The incoherent scattering measured by backscattering on a sample with deuterated ester methyl groups has revealed the single-particle motions of hydrogens in the main chain and in the R-methyl groups. Moreover, with neutron spin-echo experiments on the fully deuterated sample we have accessed the collective motions at the two first maxima of the structure factor. The simulated cell, which has been previously validated regarding the structural properties [Genix, A.-C.; et al. Macromolecules 2006, 39, 3947], shows a dynamical behavior that, allowing a shift in temperature, reproduces very accurately all the experimental results. The combined analysis of both sets of data has shown that: (i) The segmental relaxation involving backbone atoms deviates from Gaussian behavior. (ii) The dynamics is extremely heterogeneous: in addition to the subdiffusion associated with the R-process and the methyl group rotations, we have found indications of a rotational motion of the ester side group around the main chain. (iii) At a given momentum transfer and depending on the molecular groups considered, the time scales for collective motion are spread over about 1 order of magnitude, the correlations involving the main chain decaying much more slowly than those relating side groups. (iv) At the length scale characteristic for the overall periodicity of the system (that corresponding to the first structure factor peak), the experimentally observed collective dynamics relates to the backbone motions and is of interchain character; there, coherency effects are observed for all correlations, though side groups display weaker collectivity. (v) At the second structure factor peak, coherency remains only for correlations involving the main chains

Повседневность первобытного человека

Seven samples of Siluro-Devonian sedimentary rocks from the Cantabrian and Central Iberian zones of the Iberian Variscan belt have been investigated for provenance and contain four main age populations in variable relative proportion: Ediacaran–Cryogenian (c. 0.55–0.8Ga), Tonian–Stenian (0.85–1.2Ga), Palaeoproterozoic (c. 1.8–2.2Ga) and Archaean (c. 2.5–3.3Ga). Five samples contain very minor Palaeozoic (Cambrian) zircons and six samples contain minor but significant zircons of Middle and Early Mesoproterozoic (Ectasian–Calymmian, 1.6–1.8) age. These data highlight the transition from an arc environment to a stable platform following the opening of the Rheic Ocean. Variations in detrital zircon populations in Middle–Late Devonian times reflect the onset of Variscan convergence between Laurussia and Gondwana. The presence of a high proportion of zircons of Tonian–Stenian age in Devonian sedimentary rocks may be interpreted as (1) the existence of a large Tonian–Stenian arc terrane exposed in the NE African realm (in or around the Arabian–Nubian Shield), (2) the participation, from the Ordovician time, of a more easterly alongshore provenance of Tonian–Stenian zircons, and (3) an increase in the relative proportion of Tonian–Stenian zircons with respect to the Ediacaran–Cryogenian population owing to the drift of the Avalonian–Cadomian ribbon continent, or the progressive burial of Ediacaran–Cryogenian rocks coeval with the denudation of older source rocks from the craton interior