Spatial structures and dynamics of kinetically constrained models for glasses

Kob and Andersen's simple lattice models for the dynamics of structural glasses are analyzed. Although the particles have only hard core interactions, the imposed constraint that they cannot move if surrounded by too many others causes slow dynamics. On Bethe lattices a dynamical transition to a partially frozen phase occurs. In finite dimensions there exist rare mobile elements that destroy the transition. At low vacancy density, $v$, the spacing, $\Xi$, between mobile elements diverges exponentially or faster in $1/v$. Within the mobile elements, the dynamics is intrinsically cooperative and the characteristic time scale diverges faster than any power of $1/v$ (although slower than $\Xi$). The tagged-particle diffusion coefficient vanishes roughly as $\Xi^{-d}$.Comment: 4 pages. Accepted for pub. in Phys. Rev. Let

Lattice Glass Models

Motivated by the concept of geometrical frustration, we introduce a class of statistical mechanics lattice models for the glass transition. Monte Carlo simulations in three dimensions show that they display a dynamical glass transition which is very similar to that observed in other off-lattice systems and which does not depend on a specific dynamical rule. Whereas their analytic solution within the Bethe approximation shows that they do have a discontinuous glass transition compatible with the numerical observations.Comment: 4 pages, 2 figures; minor change

Real-time monitoring of protein conformational changes using a nano-mechanical sensor.

Proteins can switch between different conformations in response to stimuli, such as pH or temperature variations, or to the binding of ligands. Such plasticity and its kinetics can have a crucial functional role, and their characterization has taken center stage in protein research. As an example, Topoisomerases are particularly interesting enzymes capable of managing tangled and supercoiled double-stranded DNA, thus facilitating many physiological processes. In this work, we describe the use of a cantilever-based nanomotion sensor to characterize the dynamics of human topoisomerase II (Topo II) enzymes and their response to different kinds of ligands, such as ATP, which enhance the conformational dynamics. The sensitivity and time resolution of this sensor allow determining quantitatively the correlation between the ATP concentration and the rate of Topo II conformational changes. Furthermore, we show how to rationalize the experimental results in a comprehensive model that takes into account both the physics of the cantilever and the dynamics of the ATPase cycle of the enzyme, shedding light on the kinetics of the process. Finally, we study the effect of aclarubicin, an anticancer drug, demonstrating that it affects directly the Topo II molecule inhibiting its conformational changes. These results pave the way to a new way of studying the intrinsic dynamics of proteins and of protein complexes allowing new applications ranging from fundamental proteomics to drug discovery and development and possibly to clinical practice

Intermittency at critical transitions and aging dynamics at edge of chaos

We recall that, at both the intermittency transitions and at the Feigenbaum attractor in unimodal maps of non-linearity of order $\zeta >1$, the dynamics rigorously obeys the Tsallis statistics. We account for the $q$-indices and the generalized Lyapunov coefficients $\lambda_{q}$ that characterize the universality classes of the pitchfork and tangent bifurcations. We identify the Mori singularities in the Lyapunov spectrum at the edge of chaos with the appearance of a special value for the entropic index $q$. The physical area of the Tsallis statistics is further probed by considering the dynamics near criticality and glass formation in thermal systems. In both cases a close connection is made with states in unimodal maps with vanishing Lyapunov coefficients.Comment: Proceedings of: STATPHYS 2004 - 22nd IUPAP International Conference on Statistical Physics, National Science Seminar Complex, Indian Institute of Science, Bangalore, 4-9 July 2004. Pramana, in pres

Ubiquity of metastable-to-stable crossover in weakly chaotic dynamical systems

We present a comparative study of several dynamical systems of increasing complexity, namely, the logistic map with additive noise, one, two and many globally-coupled standard maps, and the Hamiltonian Mean Field model (i.e., the classical inertial infinitely-ranged ferromagnetically coupled XY spin model). We emphasize the appearance, in all of these systems, of metastable states and their ultimate crossover to the equilibrium state. We comment on the underlying mechanisms responsible for these phenomena (weak chaos) and compare common characteristics. We point out that this ubiquitous behavior appears to be associated to the features of the nonextensive generalization of the Boltzmann-Gibbs statistical mechanics.Comment: Communication at next2003, Second Sardinian International Conference on News and Expectations in Thermostatistics, Villasimius (Cagliari) Italy, 21st-28th September 2003. Submitted to Physica A. Elsevier Latex, 17 pages, 8 figure

Mixed matrix membranes based on torlon® and ZIF-8 for high-temperature, size-selective gas separations

Torlon® is a thermally and plasticization-resistant polyamide imide characterized by low gas permeability at room temperature. In this work, we aimed at improving the polymer performance in the thermally-enhanced He/CO2 and H2/CO2 separations, by compounding Torlon® with a highly permeable filler, ZIF-8, to fabricate Mixed Matrix Membranes (MMMs). The effect of filler loading, gas size, and temperature on the MMMs permeability, diffusivity, and selectivity was investigated. The He permeability increased by a factor of 3, while the He/CO2 selectivity decreased by a factor of 2, when adding 25 wt % of ZIF-8 at 65◦C to Torlon®; similar trends were observed for the case of H2. The MMMs permeability and size-selectivity were both enhanced by temperature. The behavior of MMMs is intermediate between the pure polymer and pure filler ones, and can be described with models for composites, indicating that such materials have a good polymer/filler adhesion and their performance could be tailored by acting on the formulation. The behavior observed is in line with previous investigations on MMMs based on glassy polymers and ZIF-8, in similar conditions, and indicates that ZIF-8 can be used as a polymer additive when the permeability is a controlling aspect, with a proper choice of loading and operative temperature

Relaxation times of kinetically constrained spin models with glassy dynamics

We analyze the density and size dependence of the relaxation time $\tau$ for kinetically constrained spin systems. These have been proposed as models for strong or fragile glasses and for systems undergoing jamming transitions. For the one (FA1f) or two (FA2f) spin facilitated Fredrickson-Andersen model at any density $\rho<1$ and for the Knight model below the critical density at which the glass transition occurs, we show that the persistence and the spin-spin time auto-correlation functions decay exponentially. This excludes the stretched exponential relaxation which was derived by numerical simulations. For FA2f in $d\geq 2$, we also prove a super-Arrhenius scaling of the form $\exp(1/(1-\rho))\leq \tau\leq\exp(1/(1-\rho)^2)$. For FA1f in $d$=$1,2$ we rigorously prove the power law scalings recently derived in \cite{JMS} while in $d\geq 3$ we obtain upper and lower bounds consistent with findings therein. Our results are based on a novel multi-scale approach which allows to analyze $\tau$ in presence of kinetic constraints and to connect time-scales and dynamical heterogeneities. The techniques are flexible enough to allow a variety of constraints and can also be applied to conservative stochastic lattice gases in presence of kinetic constraints.Comment: 4 page

Dynamical field theory for glass-forming liquids, self-consistent resummations and time-reversal symmetry

We analyse the symmetries and the self-consistent perturbative approaches of dynamical field theories for glassforming liquids. In particular, we focus on the time-reversal symmetry (TRS), which is crucial to obtain fluctuation-dissipation relations (FDRs). Previous field theoretical treatment violated this symmetry, whereas others pointed out that constructing symmetry preserving perturbation theories is a crucial and open issue. In this work we solve this problem and then apply our results to the mode-coupling theory of the glass transition (MCT). We show that in the context of dynamical field theories for glass-forming liquids TRS is expressed as a nonlinear field transformation that leaves the action invariant. Because of this nonlinearity, standard perturbation theories generically do not preserve TRS and in particular FDRs. We show how one can cure this problem and set up symmetry-preserving perturbation theories by introducing some auxiliary fields. As an outcome we obtain Schwinger-Dyson dynamical equations that automatically preserve FDRs and that serve as a basis for carrying out symmetry-preserving approximations. We apply our results to MCT, revisiting previous field theory derivations of MCT equations and showing that they generically violate FDR. We obtain symmetry-preserving mode-coupling equations and discuss their advantages and drawbacks. Furthermore, we show, contrary to previous works, that the structure of the dynamic equations is such that the ideal glass transition is not cut off at any finite order of perturbation theory, even in the presence of coupling between current and density. The opposite results found in previous field theoretical works, such as the ones based on nonlinear fluctuating hydrodynamics, were only due to an incorrect treatment of TRS.Comment: 54 pages, 21 figure

Effect of electron-phonon interaction range on lattice polaron dynamics: a continuous-time quantum Monte Carlo study

We present the numerically exact ground state energy, effective mass, and isotope exponents of a one-dimensional lattice polaron, valid for any range of electron-phonon interaction, applying a new continuous-time Quantum Monte Carlo (QMC) technique in a wide range of coupling strength and adiabatic ratio. The QMC method is free from any systematic finite-size and finite-time-step errors. We compare our numerically exact results with analytical weak-coupling theory and with the strong-coupling $1/\lambda$ expansion. We show that the exact results agree well with the canonical Fr\"ohlich and Holstein-Lang-Firsov theories in the weak and strong coupling limits, respectively, for any range of interaction. We find a strong dependence of the polaron dynamics on the range of interaction. An increased range of interaction has a similar effect to an increased (less adiabatic) phonon frequency: specifically, a reduction in the effective mass.Comment: 27 pages, 16 figures, to appear Phys Rev B. Introduction rewritten, comparison with other authors extended, description of method shortened, improved treatment of weak coupling theor