Modeling crystal growth from solution with molecular dynamics simulations: approaches to transition rate constants.

PubMed

Reilly, Anthony M; Briesen, Heiko

2012-01-21

The feasibility of using the molecular dynamics (MD) simulation technique to study crystal growth from solution quantitatively, as well as to obtain transition rate constants, has been studied. The dynamics of an interface between a solution of Lennard-Jones particles and the (100) face of an fcc lattice comprised of solute particles have been studied using MD simulations, showing that MD is, in principle, capable of following growth behavior over large supersaturation and temperature ranges. Using transition state theory, and a nearest-neighbor approximation growth and dissolution rate constants have been extracted from equilibrium MD simulations at a variety of temperatures. The temperature dependence of the rates agrees well with the expected transition state theory behavior. © 2012 American Institute of Physics

Dynamically Switching the Polarization State of Light Based on the Phase Transition of Vanadium Dioxide

NASA Astrophysics Data System (ADS)

Jia, Zhi-Yong; Shu, Fang-Zhou; Gao, Ya-Jun; Cheng, Feng; Peng, Ru-Wen; Fan, Ren-Hao; Liu, Yongmin; Wang, Mu

2018-03-01

There have been great endeavors devoted to manipulating the polarization state of light by plasmonic nanostructures in recent decades. However, the topic of active polarizers has attracted much less attention. We present a composite plasmonic nanostructure consisting of vanadium dioxide that can dynamically modulate the polarization state of the reflected light through a thermally induced phase transition of vanadium dioxide. We design a system consisting of anisotropic plasmonic nanostructures with vanadium dioxide that exhibits distinct reflections subjected to different linearly polarized incidence at room temperature and in the heated state. Under a particular linearly polarized incidence, the polarization state of the reflected light changes at room temperature, and reverts to its original polarization state above the phase-transition temperature. The composite structure can also be used to realize a dynamically switchable infrared image, wherein a pattern can be visualized at room temperature while it disappears above the phase-transition temperature. The composite structure could be potentially used for versatile optical modulators, molecular detection, and polarimetric imaging.

Effect of In-situ Cure on Measurement of Glass Transition Temperatures in High-temperature Thermosetting Polymers

DTIC Science & Technology

2015-01-01

TEMPERATURES IN HIGH-TEMPERATURE THERMOSETTING POLYMERS 5a. CONTRACT NUMBER In-House 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S...illustrated the difficulties inherent in measurement of the glass transition temperature of this high-temperature thermosetting polymer via dynamic...copyright protection in the United States. EFFECT OF IN-SITU CURE ON MEASUREMENT OF GLASS TRANSITION TEMPERATURES IN HIGH-TEMPERATURE THERMOSETTING

Glass dynamics and anomalous aging in a family of ionic liquids above the glass transition temperature.

PubMed

Shamim, Nabila; McKenna, Gregory B

2010-12-09

The present paper reports the results of a systematic rheological study of the dynamic moduli of 1-butyl 3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]), 1-butyl 3-methylimidazolium hexafluorophosphate ([Bmim][PF(6)]), and 1-ethyl 3-methylimidazolium ethylsulfate ([Emim][EtSO(4)]) in the vicinity of their respective glass transition temperatures. The results show an anomalous aging in that the dynamic and the low shear rate viscosities decrease with time at temperatures near to, but above, the glass transition temperature, and this is described. The samples that are aged into equilibrium obey the time-temperature superposition principle, and the shift factors and the viscosities follow classic super-Arrhenius behaviors with intermediate fragility values as the glass transition is approached. Similar experiments using a high-purity [Bmim][BF(4)] show that using a higher purity of the ionic liquid, while changing absolute values of the properties, does not eliminate the anomalous aging response. The data are also analyzed in a fashion similar to that used for polymer melts, and we find that these ionic liquids do not follow, for example, the Cox-Merz relationship between the steady shear viscosity and the dynamic viscosity.

Boiling regimes of impacting drops on a heated substrate under reduced pressure

NASA Astrophysics Data System (ADS)

van Limbeek, Michiel A. J.; Hoefnagels, Paul B. J.; Shirota, Minori; Sun, Chao; Lohse, Detlef

2018-05-01

We experimentally investigate the boiling behavior of impacting ethanol drops on a heated smooth sapphire substrate at pressures ranging from P =0.13 bar to atmospheric pressure. We employ frustrated total internal reflection imaging to study the wetting dynamics of the contact between the drop and the substrate. The spreading drop can be in full contact (contact boiling), it can partially touch (transition boiling), or the drop can be fully levitated (Leidenfrost boiling). We show that the temperature of the boundary between contact and transition boiling shows at most a weak dependence on the impact velocity, but a significant decrease with decreasing ambient gas pressure. A striking correspondence is found between the temperature of this boundary and the static Leidenfrost temperature for all pressures. We therefore conclude that both phenomena share the same mechanism and are dominated by the dynamics taking place at the contact line. On the other hand, the boundary between transition boiling and Leidenfrost boiling, i.e., the dynamic Leidenfrost temperature, increases for increasing impact velocity for all ambient gas pressures. Moreover, the dynamic Leidenfrost temperature coincides for pressures between P =0.13 and 0.54 bar, whereas for atmospheric pressure the dynamic Leidenfrost temperature is slightly elevated. This indicates that the dynamic Leidenfrost temperature is at most weakly dependent on the enhanced evaporation by the lower saturation temperature of the liquid.

NMR studies of water dynamics during sol-to-gel transition of poly (N-isopropylacrylamide) in concentrated aqueous solution

USDA-ARS?s Scientific Manuscript database

The thermo-sensitive polymer, poly(N-isopropylacrylamide) (PNIPAM) undergoes a coil-to-globule transition in an aqueous solution as the temperature is raised through the lower critical solution temperature. Thus far, little is known about the dynamical states of the water molecules that contribute ...

Phase diagram of the ultrafast photoinduced insulator-metal transition in vanadium dioxide

NASA Astrophysics Data System (ADS)

Cocker, T. L.; Titova, L. V.; Fourmaux, S.; Holloway, G.; Bandulet, H.-C.; Brassard, D.; Kieffer, J.-C.; El Khakani, M. A.; Hegmann, F. A.

2012-04-01

We use time-resolved terahertz spectroscopy to probe the ultrafast dynamics of the insulator-metal phase transition induced by femtosecond laser pulses in a nanogranular vanadium dioxide (VO2) film. Based on the observed thresholds for characteristic transient terahertz dynamics, a phase diagram of critical pump fluence versus temperature for the insulator-metal phase transition in VO2 is established for the first time over a broad range of temperatures down to 17 K. We find that both Mott and Peierls mechanisms are present in the insulating state and that the photoinduced transition is nonthermal. We propose a critical-threshold model for the ultrafast photoinduced transition based on a critical density of electrons and a critical density of coherently excited phonons necessary for the structural transition to the metallic state. As a result, evidence is found at low temperatures for an intermediate metallic state wherein the Mott state is melted but the Peierls distortion remains intact, consistent with recent theoretical predictions. Finally, the observed terahertz conductivity dynamics above the photoinduced transition threshold reveal nucleation and growth of metallic nanodomains over picosecond time scales.

Modulation of phase transition of thermosensitive liposomes with leucine zipper-structured lipopeptides.

PubMed

Xu, Xiejun; Xiao, Xingqing; Wang, Yiming; Xu, Shouhong; Liu, Honglai

2018-06-13

Targeted therapy for cancer requires thermosensitive components in drug carriers for controlled drug release against viral cells. The conformational transition characteristic of leucine zipper-structured lipopeptides is utilized in our lab to modulate the phase transition temperature of liposomes, thus achieving temperature-responsive control. In this study, we computationally examined the conformational transition behaviors of leucine zipper-structured lipopeptides that were modified at the N-terminus by distinct functional groups. The conformational transition temperatures of these lipopeptides were determined by structural analysis of the implicit-solvent replica exchange molecular dynamics simulation trajectories using the dihedral angle principal component analysis and the dictionary of protein secondary structure method. Our calculations revealed that the computed transition temperatures of the lipopeptides are in good agreement with the experimental measurements. The effect of hydrogen bonds on the conformational stability of the lipopeptide dimers was examined in conventional explicit-solvent molecular dynamics simulations. A quantitative correlation of the degree of structural dissociation of the dimers and their binding strength is well described by an exponential fit of the binding free energies to the conformation transition temperatures of the lipopeptides.

Temperature-Controlled High-Speed AFM: Real-Time Observation of Ripple Phase Transitions.

PubMed

Takahashi, Hirohide; Miyagi, Atsushi; Redondo-Morata, Lorena; Scheuring, Simon

2016-11-01

With nanometer lateral and Angstrom vertical resolution, atomic force microscopy (AFM) has contributed unique data improving the understanding of lipid bilayers. Lipid bilayers are found in several different temperature-dependent states, termed phases; the main phases are solid and fluid phases. The transition temperature between solid and fluid phases is lipid composition specific. Under certain conditions some lipid bilayers adopt a so-called ripple phase, a structure where solid and fluid phase domains alternate with constant periodicity. Because of its narrow regime of existence and heterogeneity ripple phase and its transition dynamics remain poorly understood. Here, a temperature control device to high-speed atomic force microscopy (HS-AFM) to observe dynamics of phase transition from ripple phase to fluid phase reversibly in real time is developed and integrated. Based on HS-AFM imaging, the phase transition processes from ripple phase to fluid phase and from ripple phase to metastable ripple phase to fluid phase could be reversibly, phenomenologically, and quantitatively studied. The results here show phase transition hysteresis in fast cooling and heating processes, while both melting and condensation occur at 24.15 °C in quasi-steady state situation. A second metastable ripple phase with larger periodicity is formed at the ripple phase to fluid phase transition when the buffer contains Ca 2+ . The presented temperature-controlled HS-AFM is a new unique experimental system to observe dynamics of temperature-sensitive processes at the nanoscopic level. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hemoglobin Dynamics in Red Blood Cells: Correlation to Body Temperature

PubMed Central

Stadler, A. M.; Digel, I.; Artmann, G. M.; Embs, J. P.; Zaccai, G.; Büldt, G.

2008-01-01

A transition in hemoglobin behavior at close to body temperature has been discovered recently by micropipette aspiration experiments on single red blood cells (RBCs) and circular dichroism spectroscopy on hemoglobin solutions. The transition temperature was directly correlated to the body temperatures of a variety of species. In an exploration of the molecular basis for the transition, we present neutron scattering measurements of the temperature dependence of hemoglobin dynamics in whole human RBCs in vivo. The data reveal a change in the geometry of internal protein motions at 36.9°C, at human body temperature. Above that temperature, amino acid side-chain motions occupy larger volumes than expected from normal temperature dependence, indicating partial unfolding of the protein. Global protein diffusion in RBCs was also measured and the findings compared favorably with theoretical predictions for short-time self-diffusion of noncharged hard-sphere colloids. The results demonstrated that changes in molecular dynamics in the picosecond time range and angstrom length scale might well be connected to a macroscopic effect on whole RBCs that occurs at body temperature. PMID:18708462

Hemoglobin dynamics in red blood cells: correlation to body temperature.

PubMed

Stadler, A M; Digel, I; Artmann, G M; Embs, J P; Zaccai, G; Büldt, G

2008-12-01

A transition in hemoglobin behavior at close to body temperature has been discovered recently by micropipette aspiration experiments on single red blood cells (RBCs) and circular dichroism spectroscopy on hemoglobin solutions. The transition temperature was directly correlated to the body temperatures of a variety of species. In an exploration of the molecular basis for the transition, we present neutron scattering measurements of the temperature dependence of hemoglobin dynamics in whole human RBCs in vivo. The data reveal a change in the geometry of internal protein motions at 36.9 degrees C, at human body temperature. Above that temperature, amino acid side-chain motions occupy larger volumes than expected from normal temperature dependence, indicating partial unfolding of the protein. Global protein diffusion in RBCs was also measured and the findings compared favorably with theoretical predictions for short-time self-diffusion of noncharged hard-sphere colloids. The results demonstrated that changes in molecular dynamics in the picosecond time range and angstrom length scale might well be connected to a macroscopic effect on whole RBCs that occurs at body temperature.

Dynamics of the α-β phase transitions in quartz and cristobalite as observed by in-situ high temperature 29Si and 17O NMR

NASA Astrophysics Data System (ADS)

Spearing, Dane R.; Farnan, Ian; Stebbins, Jonathan F.

1992-12-01

Relaxation times (T1) and lineshapes were examined as a function of temperature through the α-β transition for 29Si in a single crystal of amethyst, and for 29Si and 17O in cristobalite powders. For single crystal quartz, the three 29Si peaks observed at room temperature, representing each of the three differently oriented SiO4 tetrahedra in the unit cell, coalesce with increasing temperature such that at the α-β transition only one peak is observed. 29Si T1's decrease with increasing temperature up to the transition, above which they remain constant. Although these results are not uniquely interpretable, hopping between the Dauphiné twin related configurations, α1 and α2, may be the fluctuations responsible for both effects. This exchange becomes observable up to 150° C below the transition, and persists above the transition, resulting in β-quartz being a time and space average of α1 and α2. 29Si T1's for isotopically enriched powdered cristobalite show much the same behavior as observed for quartz. In addition, 17O T1's decrease slowly up to the α-β transition at which point there is an abrupt 1.5 order of magnitude drop. Fitting of static powder 17O spectra for cristobalite gives an asymmetry parameter (η) of 0.125 at room T, which decreases to <0.040 at the transition temperature. The electric field gradient (EFG) and chemical shift anisotropy (CSA), however, remain the same, suggesting that the decrease in η is caused by a dynamical rotation of the tetrahedra below the transition. Thus, the mechanisms of the α-β phase transitions in quartz and cristobalite are similar: there appears to be some fluctuation of the tetrahedra between twin-related orientations below the transition temperature, and the β-phase is characterized by a dynamical average of the twin domains on a unit cell scale.

Effects of dynamic heterogeneity and density scaling of molecular dynamics on the relationship among thermodynamic coefficients at the glass transition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koperwas, K., E-mail: kkoperwas@us.edu.pl; Grzybowski, A.; Grzybowska, K.

2015-07-14

In this paper, we define and experimentally verify thermodynamic characteristics of the liquid-glass transition, taking into account a kinetic origin of the process. Using the density scaling law and the four-point measure of the dynamic heterogeneity of molecular dynamics of glass forming liquids, we investigate contributions of enthalpy, temperature, and density fluctuations to spatially heterogeneous molecular dynamics at the liquid-glass transition, finding an equation for the pressure coefficient of the glass transition temperature, dTg/dp. This equation combined with our previous formula for dTg/dp, derived solely from the density scaling criterion, implies a relationship among thermodynamic coefficients at Tg. Since thismore » relationship and both the equations for dTg/dp are very well validated using experimental data at Tg, they are promising alternatives to the classical Prigogine-Defay ratio and both the Ehrenfest equations in case of the liquid-glass transition.« less

A direct ab initio molecular dynamics (MD) study on the benzophenone-water 1 : 1 complex.

PubMed

Tachikawa, Hiroto; Iyama, Tetsuji; Kato, Kohichi

2009-07-28

Direct ab initio molecular dynamics (MD) method has been applied to a benzophenone-water 1 : 1 complex Bp(H(2)O) and free benzophenone (Bp) to elucidate the effects of zero-point energy (ZPE) vibration and temperature on the absorption spectra of Bp(H(2)O). The n-pi transition of free-Bp (S(1) state) was blue-shifted by the interaction with a water molecule, whereas three pi-pi transitions (S(2), S(3) and S(4)) were red-shifted. The effects of the ZPE vibration and temperature of Bp(H(2)O) increased the intensity of the n-pi transition of Bp(H(2)O) and caused broadening of the pi-pi transitions. In case of the temperature effect, the intensity of n-pi transition increases with increasing temperature. The electronic states of Bp(H(2)O) were discussed on the basis of the theoretical results.

Non-Gaussian statistics and nanosecond dynamics of electrostatic fluctuations affecting optical transitions in proteins.

PubMed

Martin, Daniel R; Matyushov, Dmitry V

2012-08-30

We show that electrostatic fluctuations of the protein-water interface are globally non-Gaussian. The electrostatic component of the optical transition energy (energy gap) in a hydrated green fluorescent protein is studied here by classical molecular dynamics simulations. The distribution of the energy gap displays a high excess in the breadth of electrostatic fluctuations over the prediction of the Gaussian statistics. The energy gap dynamics include a nanosecond component. When simulations are repeated with frozen protein motions, the statistics shifts to the expectations of linear response and the slow dynamics disappear. We therefore suggest that both the non-Gaussian statistics and the nanosecond dynamics originate largely from global, low-frequency motions of the protein coupled to the interfacial water. The non-Gaussian statistics can be experimentally verified from the temperature dependence of the first two spectral moments measured at constant-volume conditions. Simulations at different temperatures are consistent with other indicators of the non-Gaussian statistics. In particular, the high-temperature part of the energy gap variance (second spectral moment) scales linearly with temperature and extrapolates to zero at a temperature characteristic of the protein glass transition. This result, violating the classical limit of the fluctuation-dissipation theorem, leads to a non-Boltzmann statistics of the energy gap and corresponding non-Arrhenius kinetics of radiationless electronic transitions, empirically described by the Vogel-Fulcher-Tammann law.

Dynamical arrest, percolation, gelation, and glass formation in model nanoparticle dispersions with thermoreversible adhesive interactions.

PubMed

Eberle, Aaron P R; Castañeda-Priego, Ramón; Kim, Jung M; Wagner, Norman J

2012-01-24

We report an experimental study of the dynamical arrest transition for a model system consisting of octadecyl coated silica suspended in n-tetradecane from dilute to concentrated conditions spanning the state diagram. The dispersion's interparticle potential is tuned by temperature affecting the brush conformation leading to a thermoreversible model system. The critical temperature for dynamical arrest, T*, is determined as a function of dispersion volume fraction by small-amplitude dynamic oscillatory shear rheology. We corroborate this transition temperature by measuring a power-law decay of the autocorrelation function and a loss of ergodicity via fiber-optic quasi-elastic light scattering. The structure at T* is measured using small-angle neutron scattering. The scattering intensity is fit to extract the interparticle pair-potential using the Ornstein-Zernike equation with the Percus-Yevick closure approximation, assuming a square-well interaction potential with a short-range interaction (1% of particle diameter). (1) The strength of attraction is characterized using the Baxter temperature (2) and mapped onto the adhesive hard sphere state diagram. The experiments show a continuous dynamical arrest transition line that follows the predicted dynamical percolation line until ϕ ≈ 0.41 where it subtends the predictions toward the mode coupling theory attractive-driven glass line. An alternative analysis of the phase transition through the reduced second virial coefficient B(2)* shows a change in the functional dependence of B(2)* on particle concentration around ϕ ≈ 0.36. We propose this signifies the location of a gel-to-glass transition. The results presented herein differ from those observed for depletion flocculated dispersion of micrometer-sized particles in polymer solutions, where dynamical arrest is a consequence of multicomponent phase separation, suggesting dynamical arrest is sensitive to the physical mechanism of attraction.

Hydration and temperature interdependence of protein picosecond dynamics.

PubMed

Lipps, Ferdinand; Levy, Seth; Markelz, A G

2012-05-14

We investigate the nature of the solvent motions giving rise to the rapid temperature dependence of protein picoseconds motions at 220 K, often referred to as the protein dynamical transition. The interdependence of picoseconds dynamics on hydration and temperature is examined using terahertz time domain spectroscopy to measure the complex permittivity in the 0.2-2.0 THz range for myoglobin. Both the real and imaginary parts of the permittivity over the frequency range measured have a strong temperature dependence at >0.27 h (g water per g protein), however the permittivity change is strongest for frequencies <1 THz. The temperature dependence of the real part of the permittivity is not consistent with the relaxational response of the bound water, and may reflect the low frequency protein structural vibrations slaved to the solvent excitations. The hydration necessary to observe the dynamical transition is found to be frequency dependent, with a critical hydration of 0.19 h for frequencies >1 THz, and 0.27 h for frequencies <1 THz. The data are consistent with the dynamical transition solvent fluctuations requiring only clusters of ~5 water molecules, whereas the enhancement of lowest frequency motions requires a fully spanning water network. This journal is © the Owner Societies 2012

Ultrafast Dynamics in Vanadium Dioxide: Separating Spatially Segregated Mixed Phase Dynamics in the Time-domain

NASA Astrophysics Data System (ADS)

Hilton, David

2011-10-01

In correlated electronic systems, observed electronic and structural behavior results from the complex interplay between multiple, sometimes competing degrees-of- freedom. One such material used to study insulator-to-metal transitions is vanadium dioxide, which undergoes a phase transition from a monoclinic-insulating phase to a rutile-metallic phase when the sample is heated to 340 K. The major open question with this material is the relative influence of this structural phase transition (Peirels transition) and the effects of electronic correlations (Mott transition) on the observed insulator-to-metal transition. Answers to these major questions are complicated by vanadium dioxide's sensitivity to perturbations in the chemical structure in VO2. For example, related VxOy oxides with nearly a 2:1 ratio do not demonstrate the insulator-to- metal transition, while recent work has demonstrated that W:VO2 has demonstrated a tunable transition temperature controllable with tungsten doping. All of these preexisting results suggest that the observed electronic properties are exquisitely sensitive to the sample disorder. Using ultrafast spectroscopic techniques, it is now possible to impulsively excite this transition and investigate the photoinduced counterpart to this thermal phase transition in a strongly nonequilibrium regime. I will discuss our recent results studying the terahertz-frequency conductivity dynamics of this photoinduced phase transition in the poorly understood near threshold temperature range. We find a dramatic softening of the transition near the critical temperature, which results primarily from the mixed phase coexistence near the transition temperature. To directly study this mixed phase behavior, we directly study the nucleation and growth rates of the metallic phase in the parent insulator using non-degenerate optical pump-probe spectroscopy. These experiments measure, in the time- domain, the coexistent phase separation in VO2 (spatially separated insulator and metal islands) and, more importantly, their dynamic evolution in response to optical excitation.

Dynamical arrest with zero complexity: The unusual behavior of the spherical Blume-Emery-Griffiths disordered model

NASA Astrophysics Data System (ADS)

Rainone, Corrado; Ferrari, Ulisse; Paoluzzi, Matteo; Leuzzi, Luca

2015-12-01

The short- and long-time dynamics of model systems undergoing a glass transition with apparent inversion of Kauzmann and dynamical arrest glass transition lines is investigated. These models belong to the class of the spherical mean-field approximation of a spin-1 model with p -body quenched disordered interaction, with p >2 , termed spherical Blume-Emery-Griffiths models. Depending on temperature and chemical potential the system is found in a paramagnetic or in a glassy phase and the transition between these phases can be of a different nature. In specific regions of the phase diagram coexistence of low-density and high-density paramagnets can occur, as well as the coexistence of spin-glass and paramagnetic phases. The exact static solution for the glassy phase is known to be obtained by the one-step replica symmetry breaking ansatz. Different scenarios arise for both the dynamic and the thermodynamic transitions. These include: (i) the usual random first-order transition (Kauzmann-like) for mean-field glasses preceded by a dynamic transition, (ii) a thermodynamic first-order transition with phase coexistence and latent heat, and (iii) a regime of apparent inversion of static transition line and dynamic transition lines, the latter defined as a nonzero complexity line. The latter inversion, though, turns out to be preceded by a dynamical arrest line at higher temperature. Crossover between different regimes is analyzed by solving mode-coupling-theory equations near the boundaries of paramagnetic solutions and the relationship with the underlying statics is discussed.

Dynamical transition for a particle in a squared Gaussian potential

NASA Astrophysics Data System (ADS)

Touya, C.; Dean, D. S.

2007-02-01

We study the problem of a Brownian particle diffusing in finite dimensions in a potential given by ψ = phi2/2 where phi is Gaussian random field. Exact results for the diffusion constant in the high temperature phase are given in one and two dimensions and it is shown to vanish in a power-law fashion at the dynamical transition temperature. Our results are confronted with numerical simulations where the Gaussian field is constructed, in a standard way, as a sum over random Fourier modes. We show that when the number of Fourier modes is finite the low temperature diffusion constant becomes non-zero and has an Arrhenius form. Thus we have a simple model with a fully understood finite size scaling theory for the dynamical transition. In addition we analyse the nature of the anomalous diffusion in the low temperature regime and show that the anomalous exponent agrees with that predicted by a trap model.

Characterization of the low-temperature properties of a simplified protein model

NASA Astrophysics Data System (ADS)

Hagmann, Johannes-Geert; Nakagawa, Naoko; Peyrard, Michel

2014-01-01

Prompted by results that showed that a simple protein model, the frustrated Gō model, appears to exhibit a transition reminiscent of the protein dynamical transition, we examine the validity of this model to describe the low-temperature properties of proteins. First, we examine equilibrium fluctuations. We calculate its incoherent neutron-scattering structure factor and show that it can be well described by a theory using the one-phonon approximation. By performing an inherent structure analysis, we assess the transitions among energy states at low temperatures. Then, we examine nonequilibrium fluctuations after a sudden cooling of the protein. We investigate the violation of the fluctuation-dissipation theorem in order to analyze the protein glass transition. We find that the effective temperature of the quenched protein deviates from the temperature of the thermostat, however it relaxes towards the actual temperature with an Arrhenius behavior as the waiting time increases. These results of the equilibrium and nonequilibrium studies converge to the conclusion that the apparent dynamical transition of this coarse-grained model cannot be attributed to a glassy behavior.

Effect of Cation Rotation on Charge Dynamics in Hybrid Lead Halide Perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gélvez-Rueda, María C.; Cao, Duyen H.; Patwardhan, Sameer

Organic-inorganic hybrid halide perovskites are a promising class of materials for photovoltaic application with reported power efficiencies over similar to 22%. However, not much is known about the influence of the organic dipole rotation and phase transitions on charge carrier dynamics. Here, we report substantial changes in mobility and lifetime of charge carriers in CH 3NH 3PbI 3 after the low-temperature tetragonal (beta) to orthorhombic (gamma) phase transition. By using microwave conductivity measurements, we observed that the mobility and lifetime of ionized charge carriers increase as the temperature decreases and a sudden increment is seen after the beta-gamma phase transition.more » For CH 3NH 3PbI 3, the mobility and the half-lifetime increase by a factor of 36 compared with the values before the beta-gamma phase transition. We attribute the considerable change in the dynamics at low temperature to the decrease of the inherent dynamic disorder of the organic cation (CH 3NH 3+) inside the perovskite crystal structure.« less

Mechanical relaxations of a Cu60Zr40 metallic glass studied by using a dynamic mechanical analysis

NASA Astrophysics Data System (ADS)

Jeong, H. T.; Park, C. O.

2013-03-01

The mechanical relaxation behaviors of a Cu60Zr40 metallic glass were investigated by using isothermal multi-frequency dynamic mechanical measurements. From the spectra of the elastic moduli, master curves were constructed using the time-temperature superposition principle. The temperature dependence of the shift factor was found to follow the Arrhenius relationship in two temperature regions, one below and the other above the glass transition temperature ( T g ), and the activation energies for low-temperature relaxation and viscous flow were 32.7 kJ/mol and 307.1 kJ/mol, respectively. The decoupling of these two relaxations, shown in the temperature dependent plot of the shift factor, manifests the dynamic glass transition temperature region of the Cu60Zr40 metallic glass. From the temperature dependence of the shift factor, the fragility index of this alloy was also estimated.

Polymer brushes: a controllable system with adjustable glass transition temperature of fragile glass formers.

PubMed

Xie, Shi-Jie; Qian, Hu-Jun; Lu, Zhong-Yuan

2014-01-28

We present results of molecular dynamics simulations for coarse-grained polymer brushes in a wide temperature range to investigate the factors that affect the glass transition in these systems. We focus on the influences of free surface, polymer-substrate interaction strength, grafting density, and chain length not only on the change of glass transition temperature Tg, but also the fragility D of the glass former. It is found that the confinement can enhance the dependence of the Tg on the cooling rate as compared to the bulk melt. Our layer-resolved analysis demonstrates that it is possible to control the glass transition temperature Tg of polymer brushes by tuning the polymer-substrate interaction strength, the grafting density, and the chain length. Moreover, we find quantitative differences in the influence range of the substrate and the free surface on the density and dynamics. This stresses the importance of long range cooperative motion in glass formers near the glass transition temperature. Furthermore, the string-like cooperative motion analysis demonstrates that there exists a close relation among glass transition temperature Tg, fragility D, and string length ⟨S⟩. The polymer brushes that possess larger string length ⟨S⟩ tend to have relatively higher Tg and smaller D. Our results suggest that confining a fragile glass former through forming polymer brushes changes not only the glass transition temperature Tg, but also the very nature of relaxation process.

Microscopic relaxations in a protein sustained down to 160K in a non-glass forming organic solvent.

PubMed

Mamontov, E; O'Neill, H

2017-01-01

We have studied microscopic dynamics of a protein in carbon disulfide, a non-glass forming solvent, down to its freezing temperature of ca. 160K. We have utilized quasielastic neutron scattering. A comparison of lysozyme hydrated with water and dissolved in carbon disulfide reveals a stark difference in the temperature dependence of the protein's microscopic relaxation dynamics induced by the solvent. In the case of hydration water, the common protein glass-forming solvent, the protein relaxation slows down in response to a large increase in the water viscosity on cooling down, exhibiting a well-known protein dynamical transition. The dynamical transition disappears in non-glass forming carbon disulfide, whose viscosity remains a weak function of temperature all the way down to freezing at just below 160K. The microscopic relaxation dynamics of lysozyme dissolved in carbon disulfide is sustained down to the freezing temperature of its solvent at a rate similar to that measured at ambient temperature. Our results demonstrate that protein dynamical transition is not merely solvent-assisted, but rather solvent-induced, or, more precisely, is a reflection of the temperature dependence of the solvent's glass-forming dynamics. We hypothesize that, if the long debated idea regarding the direct link between the microscopic relaxations and the biological activity in proteins is correct, then not only the microscopic relaxations, but also the activity, could be sustained in proteins all the way down to the freezing temperature of a non-glass forming solvent with a weak temperature dependence of its viscosity. This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazù and Dr. Federica Migliardo. Copyright © 2016 Elsevier B.V. All rights reserved.

Tribological Behavior and the Mild–Severe Wear Transition of Mg97Zn1Y2 Alloy with a LPSO Structure Phase

PubMed Central

Sun, Wei; Xuan, Xihua; Li, Liang; An, Jian

2018-01-01

Dry friction and wear tests were performed on as-cast Mg97Zn1Y2 alloy using a pin-on-disc configuration. Coefficients of friction and wear rates were measured as a function of applied load at sliding speeds of 0.2, 0.8 and 3.0 m/s. The wear mechanisms were identified in the mild and severe wear regimes by means of morphological observation and composition analysis of worn surfaces using scanning electron microscope (SEM) and energy dispersive X-ray spectrometer (EDS). Analyses of microstructure and hardness changes in subsurfaces verified the microstructure transformation from the deformed to the dynamically recrystallized, and properties changed from the strain hardening to dynamic crystallization (DRX) softening before and after the mild–severe wear transition. The mild–severe wear transition can be determined by a proposed contact surface DRX temperature criterion, from which the critical DRX temperatures at different sliding speeds are calculated using DRX dynamics; hence transition loads can also be calculated using a transition load model. The calculated transition loads are in good agreement with the measured ones, demonstrating the validity and applicability of the contact surface DRX temperature criterion. PMID:29584692

New Insights into the Molecular Dynamics of P3HT:PCBM Bulk Heterojunction: A Time-of-Flight Quasi-Elastic Neutron Scattering Study.

PubMed

Guilbert, Anne A Y; Zbiri, Mohamed; Jenart, Maud V C; Nielsen, Christian B; Nelson, Jenny

2016-06-16

The molecular dynamics of organic semiconductor blend layers are likely to affect the optoelectronic properties and the performance of devices such as solar cells. We study the dynamics (5-50 ps) of the poly(3-hexylthiophene) (P3HT): phenyl-C61-butyric acid methyl ester (PCBM) blend by time-of-flight quasi-elastic neutron scattering, at temperatures in the range 250-360 K, thus spanning the glass transition temperature region of the polymer and the operation temperature of an OPV device. The behavior of the QENS signal provides evidence for the vitrification of P3HT upon blending, especially above the glass transition temperature, and the plasticization of PCBM by P3HT, both dynamics occurring on the picosecond time scale.

Glassy behavior and dynamic tweed in defect-free multiferroics

NASA Astrophysics Data System (ADS)

Wang, Xiaofei; Salje, Ekhard K. H.; Sun, Jun; Ding, Xiangdong

2018-01-01

Multiferroics often show significant elastic fluctuations even when the transition is strongly stepwise. Molecular dynamics simulations of a generic toy model show the appearance of tweed nanostructures (cross hatched patterns) in the paraelastic phase just above the transition point. This tweed lowers the elastic modulus C12 when approaching the transition temperature. The spatial and temporal correlations of the tweed structure follow the Vogel-Fulcher relationship, and the Vogel-Fulcher temperature is slightly below the transition temperature Ttrans, preventing this glassy state to freeze completely. Spatial correlations of shear strain show that the size of tweed patches reaches about eight lattice spacings near Ttrans. Cross- and rod-shaped diffuse scattering, similar to that in relaxors, emerges around {hh0}* and {h00}* Bragg reflections. The viscosity of the sample increases dramatically at the transition point with a significant precursor increase in the tweed regime.

Cooperative structural transitions in amyloid-like aggregation

NASA Astrophysics Data System (ADS)

Steckmann, Timothy; Bhandari, Yuba R.; Chapagain, Prem P.; Gerstman, Bernard S.

2017-04-01

Amyloid fibril aggregation is associated with several horrific diseases such as Alzheimer's, Creutzfeld-Jacob, diabetes, Parkinson's, and others. Although proteins that undergo aggregation vary widely in their primary structure, they all produce a cross-β motif with the proteins in β-strand conformations perpendicular to the fibril axis. The process of amyloid aggregation involves forming myriad different metastable intermediate aggregates. To better understand the molecular basis of the protein structural transitions and aggregation, we report on molecular dynamics (MD) computational studies on the formation of amyloid protofibrillar structures in the small model protein ccβ, which undergoes many of the structural transitions of the larger, naturally occurring amyloid forming proteins. Two different structural transition processes involving hydrogen bonds are observed for aggregation into fibrils: the breaking of intrachain hydrogen bonds to allow β-hairpin proteins to straighten, and the subsequent formation of interchain H-bonds during aggregation into amyloid fibrils. For our MD simulations, we found that the temperature dependence of these two different structural transition processes results in the existence of a temperature window that the ccβ protein experiences during the process of forming protofibrillar structures. This temperature dependence allows us to investigate the dynamics on a molecular level. We report on the thermodynamics and cooperativity of the transformations. The structural transitions that occurred in a specific temperature window for ccβ in our investigations may also occur in other amyloid forming proteins but with biochemical parameters controlling the dynamics rather than temperature.

Viscoelastic properties of addition-cured polyimides used in high temperature polymer matrix composites

NASA Technical Reports Server (NTRS)

Roberts, Gary D.; Malarik, Diane C.; Robaidek, Jerrold O.

1991-01-01

The viscoelastic properties of an addition-cured polyimide, PMR-15, were evaluated through dynamic mechanical and stress relaxation testing. Below the glass transition temperature, the dynamic mechanical properties of the composites are strongly affected by the absorbed moisture in the resin. At temperature 20 C and more above the glass transition temperature, the storage modulus increases continuously with time, indicating that additional crosslinking is occurring in the resin. For resin moisture contents less than 2 percent, stress relaxation curves measured at different temperatures can be superimposed using horizontal shifts along the log(time) axis with only small shifts along the vertical axis.

Structure and collective dynamics of hydrated anti-freeze protein type III from 180 K to 298 K by X-ray diffraction and inelastic X-ray scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoshida, Koji; Baron, Alfred Q. R.; Uchiyama, Hiroshi

We investigated hydrated antifreeze protein type III (AFP III) powder with a hydration level h (=mass of water/mass of protein) of 0.4 in the temperature range between 180 K and 298 K using X-ray diffraction and inelastic X-ray scattering (IXS). The X-ray diffraction data showed smooth, largely monotonic changes between 180 K and 298 K without freezing water. Meanwhile, the collective dynamics observed by IXS showed a strong change in the sound velocity at 180 K, after being largely temperature independent at higher temperatures (298–220 K). We interpret this change in terms of the dynamic transition previously discussed using othermore » probes including THz IR absorption spectroscopy and incoherent elastic and quasi-elastic neutron scattering. This finding suggests that the dynamic transition of hydrated proteins is observable on the subpicosecond time scale as well as nano- and pico-second scales, both in collective dynamics from IXS and single particle dynamics from neutron scattering. Moreover, it is most likely that the dynamic transition of hydrated AFP III is not directly correlated with its hydration structure.« less

Structure and collective dynamics of hydrated anti-freeze protein type III from 180 K to 298 K by X-ray diffraction and inelastic X-ray scattering

NASA Astrophysics Data System (ADS)

Yoshida, Koji; Baron, Alfred Q. R.; Uchiyama, Hiroshi; Tsutsui, Satoshi; Yamaguchi, Toshio

2016-04-01

We investigated hydrated antifreeze protein type III (AFP III) powder with a hydration level h (=mass of water/mass of protein) of 0.4 in the temperature range between 180 K and 298 K using X-ray diffraction and inelastic X-ray scattering (IXS). The X-ray diffraction data showed smooth, largely monotonic changes between 180 K and 298 K without freezing water. Meanwhile, the collective dynamics observed by IXS showed a strong change in the sound velocity at 180 K, after being largely temperature independent at higher temperatures (298-220 K). We interpret this change in terms of the dynamic transition previously discussed using other probes including THz IR absorption spectroscopy and incoherent elastic and quasi-elastic neutron scattering. This finding suggests that the dynamic transition of hydrated proteins is observable on the subpicosecond time scale as well as nano- and pico-second scales, both in collective dynamics from IXS and single particle dynamics from neutron scattering. Moreover, it is most likely that the dynamic transition of hydrated AFP III is not directly correlated with its hydration structure.

Structure and collective dynamics of hydrated anti-freeze protein type III from 180 K to 298 K by X-ray diffraction and inelastic X-ray scattering.

PubMed

Yoshida, Koji; Baron, Alfred Q R; Uchiyama, Hiroshi; Tsutsui, Satoshi; Yamaguchi, Toshio

2016-04-07

We investigated hydrated antifreeze protein type III (AFP III) powder with a hydration level h (=mass of water/mass of protein) of 0.4 in the temperature range between 180 K and 298 K using X-ray diffraction and inelastic X-ray scattering (IXS). The X-ray diffraction data showed smooth, largely monotonic changes between 180 K and 298 K without freezing water. Meanwhile, the collective dynamics observed by IXS showed a strong change in the sound velocity at 180 K, after being largely temperature independent at higher temperatures (298-220 K). We interpret this change in terms of the dynamic transition previously discussed using other probes including THz IR absorption spectroscopy and incoherent elastic and quasi-elastic neutron scattering. This finding suggests that the dynamic transition of hydrated proteins is observable on the subpicosecond time scale as well as nano- and pico-second scales, both in collective dynamics from IXS and single particle dynamics from neutron scattering. Moreover, it is most likely that the dynamic transition of hydrated AFP III is not directly correlated with its hydration structure.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanz, Alejandro; Ezquerra, Tiberio A.; Nogales, Aurora, E-mail: aurora.nogales@csic.es

The dynamics of lower disorder-order temperature diblock copolymer leading to phase separation has been observed by X ray photon correlation spectroscopy. Two different modes have been characterized. A non-diffusive mode appears at temperatures below the disorder to order transition, which can be associated to compositional fluctuations, that becomes slower as the interaction parameter increases, in a similar way to the one observed for diblock copolymers exhibiting phase separation upon cooling. At temperatures above the disorder to order transition T{sub ODT}, the dynamics becomes diffusive, indicating that after phase separation in Lower Disorder-Order Transition (LDOT) diblock copolymers, the diffusion of chainmore » segments across the interface is the governing dynamics. As the segregation is stronger, the diffusive process becomes slower. Both observed modes have been predicted by the theory describing upper order-disorder transition systems, assuming incompressibility. However, the present results indicate that the existence of these two modes is more universal as they are present also in compressible diblock copolymers exhibiting a lower disorder-order transition. No such a theory describing the dynamics in LDOT block copolymers is available, and these experimental results may offer some hints to understanding the dynamics in these systems. The dynamics has also been studied in the ordered state, and for the present system, the non-diffusive mode disappears and only a diffusive mode is observed. This mode is related to the transport of segment in the interphase, due to the weak segregation on this system.« less

The glass transition temperature of thin films: A molecular dynamics study for a bead-spring model.

PubMed

Stevenson, Craig S; Curro, John G; McCoy, John D

2017-05-28

Molecular dynamics simulations were carried out on free-standing liquid films of different thicknesses h using a bead-spring model of 10 beads per chain. The glass transition temperatures, T g , of the various films were determined from plots of the internal energy versus temperature. We used these simulations to test the validity of our earlier conjecture that the glass transition of a confined liquid could be approximated by pre-averaging over the non-uniform density profile of the film. Using the density profiles from our simulations, we computed the average density of the free-standing films as a function of temperature. In all our film simulations we found, within the error of the simulation, that T g of the film occurred at the same density (or packing fraction) as the bulk system at the bulk glass transition temperature T g B . By equating these densities at their respective glass transition temperatures, as suggested by the simulations, we deduced that T g /T g B is proportional to h 0 /h. This is consistent with previous simulations and experimental data. Moreover, the parameter h 0 is determinable in our model from the density profile of the films.

Dynamics of water in LiCl and CaCl 2 aqueous solutions confined in silica matrices: A backscattering neutron spectroscopy study

NASA Astrophysics Data System (ADS)

Mamontov, E.; Cole, D. R.; Dai, S.; Pawel, M. D.; Liang, C. D.; Jenkins, T.; Gasparovic, G.; Kintzel, E.

2008-09-01

Backscattering neutron spectroscopy was used to probe the dynamics of water molecules in LiCl and CaCl 2 aqueous solutions confined in 2.7, 1.9, and 1.4 nm diameter pores of various silica matrices. The pore size of 2.7 nm was found to be sufficiently large for the confined liquids to exhibit characteristic traits of bulk behavior, such as a freezing-melting transition and a phase separation. On the other hand, none of the fluids in the 1.4 nm pores exhibited a clear freezing-melting transition; instead, their dynamics at low temperatures gradually became too slow for the nanosecond resolution of the experiment. The greatest suppression of water mobility was observed in the CaCl 2 solutions, which suggests that cation charge and perhaps the cation hydration environment have a profound influence on the dynamics of the water molecules. Quasielastic neutron scattering measurements of pure H 2O and 1 m LiCl-H 2O solution confined in 1.9 nm pores revealed a dynamic transition in both liquids at practically the same temperature of 225-226 K, even though the dynamics of the solution at room temperature appeared to slow down by more than an order of magnitude compared to the pure water. The observation of the dynamic transition in the solution suggests that this transition may be a universal feature of water governed by processes acting on the local scale, such as a change in the hydrogen bonding.

Fragile-to-strong transition in liquid silica

NASA Astrophysics Data System (ADS)

Geske, Julian; Drossel, Barbara; Vogel, Michael

2016-03-01

We investigate anomalies in liquid silica with molecular dynamics simulations and present evidence for a fragile-to-strong transition at around 3100 K-3300 K. To this purpose, we studied the structure and dynamical properties of silica over a wide temperature range, finding four indicators of a fragile-to-strong transition. First, there is a density minimum at around 3000 K and a density maximum at 4700 K. The turning point is at 3400 K. Second, the local structure characterized by the tetrahedral order parameter changes dramatically around 3000 K from a higher-ordered, lower-density phase to a less ordered, higher-density phase. Third, the correlation time τ changes from an Arrhenius behavior below 3300 K to a Vogel-Fulcher-Tammann behavior at higher temperatures. Fourth, the Stokes-Einstein relation holds for temperatures below 3000 K, but is replaced by a fractional relation above this temperature. Furthermore, our data indicate that dynamics become again simple above 5000 K, with Arrhenius behavior and a classical Stokes-Einstein relation.

Dynamical Transition of Collective Motions in Dry Proteins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Zhuo; Huang, Juan; Tyagi, Madhusudan

Water is widely assumed to be essential for protein dynamics and function. In particular, the well-documented “dynamical” transition at ~ 200 K , at which the protein changes from a rigid, nonfunctional form to a flexible, functional state, as detected in hydrogenated protein by incoherent neutron scattering, requires hydration. We report on coherent neutron scattering experiments on perdeuterated proteins and reveal that a transition occurs in dry proteins at the same temperature resulting primarily from the collective heavy-atom motions. Furthermore, the dynamical transition discovered is intrinsic to the energy landscape of dry proteins.

Dynamical Transition of Collective Motions in Dry Proteins

DOE PAGES

Liu, Zhuo; Huang, Juan; Tyagi, Madhusudan; ...

2017-07-25

Water is widely assumed to be essential for protein dynamics and function. In particular, the well-documented “dynamical” transition at ~ 200 K , at which the protein changes from a rigid, nonfunctional form to a flexible, functional state, as detected in hydrogenated protein by incoherent neutron scattering, requires hydration. We report on coherent neutron scattering experiments on perdeuterated proteins and reveal that a transition occurs in dry proteins at the same temperature resulting primarily from the collective heavy-atom motions. Furthermore, the dynamical transition discovered is intrinsic to the energy landscape of dry proteins.

Dynamic mechanical analysis of fiber reinforced composites

NASA Technical Reports Server (NTRS)

Reed, K. E.

1979-01-01

Dynamic mechanical and thermal properties were determined for unidirectional epoxy/glass composites at various fiber orientation angles. Resonant frequency and relative logarithmic decrement were measured as functions of temperature. In low angle and longitudinal specimens a transition was observed above the resin glass transition temperature which was manifested mechanically as an additional damping peak and thermally as a change in the coefficient of thermal expansion. The new transition was attributed to a heterogeneous resin matrix induced by the fiber. The temperature span of the glass-rubber relaxation was found to broaden with decreasing orientation angle, reflecting the growth of fiber contribution and exhibiting behavior similar to that of Young's modulus. The change in resonant frequency through the glass transition was greatest for samples of intermediate fiber angle, demonstrating behavior similar to that of the longitudinal shear modulus.

Instantaneous Normal Modes and the Protein Glass Transition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schulz, Roland; Krishnan, Marimuthu; Daidone, Isabella

2009-01-01

In the instantaneous normal mode method, normal mode analysis is performed at instantaneous configurations of a condensed-phase system, leading to modes with negative eigenvalues. These negative modes provide a means of characterizing local anharmonicities of the potential energy surface. Here, we apply instantaneous normal mode to analyze temperature-dependent diffusive dynamics in molecular dynamics simulations of a small protein (a scorpion toxin). Those characteristics of the negative modes are determined that correlate with the dynamical (or glass) transition behavior of the protein, as manifested as an increase in the gradient with T of the average atomic mean-square displacement at ~ 220more » K. The number of negative eigenvalues shows no transition with temperature. Further, although filtering the negative modes to retain only those with eigenvectors corresponding to double-well potentials does reveal a transition in the hydration water, again, no transition in the protein is seen. However, additional filtering of the protein double-well modes, so as to retain only those that, on energy minimization, escape to different regions of configurational space, finally leads to clear protein dynamical transition behavior. Partial minimization of instantaneous configurations is also found to remove nondiffusive imaginary modes. In summary, examination of the form of negative instantaneous normal modes is shown to furnish a physical picture of local diffusive dynamics accompanying the protein glass transition.« less

Instantaneous Normal Modes and the Protein Glass Transition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schultz, Roland; Krishnan, Marimuthu; Daidone, Isabella

2009-01-01

In the instantaneous normal mode method, normal mode analysis is performed at instantaneous configurations of a condensed-phase system, leading to modes with negative eigenvalues. These negative modes provide a means of characterizing local anharmonicities of the potential energy surface. Here, we apply instantaneous normal mode to analyze temperature-dependent diffusive dynamics in molecular dynamics simulations of a small protein (a scorpion toxin). Those characteristics of the negative modes are determined that correlate with the dynamical (or glass) transition behavior of the protein, as manifested as an increase in the gradient with T of the average atomic mean-square displacement at 220 K.more » The number of negative eigenvalues shows no transition with temperature. Further, although filtering the negative modes to retain only those with eigenvectors corresponding to double-well potentials does reveal a transition in the hydration water, again, no transition in the protein is seen. However, additional filtering of the protein double-well modes, so as to retain only those that, on energy minimization, escape to different regions of configurational space, finally leads to clear protein dynamical transition behavior. Partial minimization of instantaneous configurations is also found to remove nondiffusive imaginary modes. In summary, examination of the form of negative instantaneous normal modes is shown to furnish a physical picture of local diffusive dynamics accompanying the protein glass transition.« less

Effect of In-Situ Cure on Measurement of Glass Transition Temperatures in High-Temperature Thermosetting Polymers (Briefing Charts)

DTIC Science & Technology

2015-05-20

TEMPERATURES IN HIGH-TEMPERATURE THERMOSETTING POLYMERS 5a. CONTRACT NUMBER In-House 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d...temperature thermosetting polymer via dynamic mechanical analysis alone. These difficulties result from the residual cure of samples heated beyond their...98) Prescribed by ANSI Std. 239.18 Effect of In-Situ Cure on Measurement of Glass Transition Temperatures in High-Temperature Thermosetting

Striking role of non-bridging oxygen on glass transition temperature of calcium aluminosilicate glass-formers

NASA Astrophysics Data System (ADS)

Bouhadja, M.; Jakse, N.; Pasturel, A.

2014-06-01

Molecular dynamics simulations are used to study the structural and dynamic properties of calcium aluminosilicate, (CaO-Al2O3)1-x(SiO2)x, glass formers along three joins, namely, R = 1, 1.57, and 3, in which the silica content x can vary from 0 to 1. For all compositions, we determined the glass-transition temperature, the abundances of the non-bridging oxygen, triclusters, and AlO5 structural units, as well as the fragility from the temperature evolution of the α-relaxation times. We clearly evidence the role played by the non-bridging oxygen linked either to Al atoms or Si atoms in the evolution of the glass-transition temperature as well as of the fragility as a function of silica content along the three joins.

Glass transition dynamics and conductivity scaling in ionic deep eutectic solvents: The case of (acetamide + lithium nitrate/sodium thiocyanate) melts.

PubMed

Tripathy, Satya N; Wojnarowska, Zaneta; Knapik, Justyna; Shirota, Hideaki; Biswas, Ranjit; Paluch, Marian

2015-05-14

A detailed investigation on the molecular dynamics of ionic deep eutectic solvents (acetamide + lithium nitrate/sodium thiocyanate) is reported. The study was carried out employing dielectric relaxation spectroscopy covering seven decades in frequency (10(-1)-10(6) Hz) and in a wide temperature range from 373 K down to 173 K, accessing the dynamic observables both in liquid and glassy state. The dielectric response of the ionic system has been presented in the dynamic window of modulus formalism to understand the conductivity relaxation and its possible connection to the origin of localized motion. Two secondary relaxation processes appear below glass transition temperature. Our findings provide suitable interpretation on the nature of secondary Johari-Goldstein process describing the ion translation and orientation of dipoles in a combined approach using Ngai's coupling model. A nearly constant loss feature is witnessed at shorter times/lower temperatures. We also discuss the ac conductivity scaling behavior using Summerfield approach and random free energy barrier model which establish the time-temperature superposition principle. These experimental observations have fundamental importance on theoretical elucidation of the conductivity relaxation and glass transition phenomena in molten ionic conductors.

Microscopic Chain Motion in Polymer Nanocomposites with Dynamically Asymmetric Interphases

PubMed Central

Senses, Erkan; Faraone, Antonio; Akcora, Pinar

2016-01-01

Dynamics of the interphase region between matrix and bound polymers on nanoparticles is important to understand the macroscopic rheological properties of nanocomposites. Here, we present neutron scattering investigations on nanocomposites with dynamically asymmetric interphases formed by a high-glass transition temperature polymer, poly(methyl methacrylate), adsorbed on nanoparticles and a low-glass transition temperature miscible matrix, poly(ethylene oxide). By taking advantage of selective isotope labeling of the chains, we studied the role of interfacial polymer on segmental and collective dynamics of the matrix chains from subnanoseconds to 100 nanoseconds. Our results show that the Rouse relaxation remains unchanged in a weakly attractive composite system while the dynamics significantly slows down in a strongly attractive composite. More importantly, the chains disentangle with a remarkable increase of the reptation tube size when the bound polymer is vitreous. The glassy and rubbery states of the bound polymer as temperature changes underpin the macroscopic stiffening of nanocomposites. PMID:27457056

Dynamics of molecular rotors confined in two dimensions: transition from a 2D rotational glass to a 2D rotational fluid in a periodic mesoporous organosilica.

PubMed

Vogelsberg, Cortnie S; Bracco, Silvia; Beretta, Mario; Comotti, Angiolina; Sozzani, Piero; Garcia-Garibay, Miguel A

2012-02-09

The motional behavior of p-phenylene-d(4) rotators confined within the 2D layers of a hierarchically ordered periodic mesoporous p-divinylbenzenesilica has been elucidated to evaluate the effects of reduced dimensionality on the engineered dynamics of artificial molecular machines. The hybrid mesoporous material, characterized by a honeycomb lattice structure, has arrays of alternating p-divinylbenzene rotors and siloxane layers forming the molecularly ordered walls of the mesoscopic channels. The p-divinylbenzene rotors are strongly anchored between two adjacent siloxane sheets, so that the p-phenylene rotators are unable to experience translational diffusion and are allowed to rotate about only one fixed axis. Variable-temperature (2)H NMR experiments revealed that the p-phenylene rotators undergo an exchange process between sites related by 180° and a non-Arrhenius temperature dependence of the dynamics, with reorientational rates ranging from 10(3) to 10(8) Hz between 215 to 305 K. The regime of motion changes rapidly at about 280 K indicating the occurrence of a dynamical transition. The transition was also recognized by a steep change in the heat capacity at constant pressure. As a result of the robust lamellar architecture comprising the pore walls, the orientational dynamic disorder related to the phase transition is only realized in two dimensions within the layers, that is in the plane perpendicular to the channel axis. Thus, the aligned rotors that form the organic layers exhibit unique anisotropic dynamical properties as a result of the architecture's reduced dimensionality. The dynamical disorder restricted to two dimensions constitutes a highly mobile fluidlike rotational phase at room temperature, which upon cooling undergoes a transition to a more rigid glasslike phase. Activation energies of 5.9 and 9.5 kcal/mol respectively have been measured for the two dynamical regimes of rotation. Collectively, our investigation has led to the discovery of an orientationally disordered 2D rotational glass and its transition from rigid to soft at increasing temperature. The spectral narrowing observed in the (2)H NMR experiments at higher temperatures (310-420 K) is consistent with fast rotational dynamics, which remain anisotropic in nature within the robust lamellar architecture. This study suggests that exploiting reduced dimensionality in the design of solid-state artificial molecular machines and functional materials may yield access to behavior previously unrealized in 3D materials. © 2012 American Chemical Society

Bose–Einstein condensation versus Dicke–Hepp–Lieb transition in an optical cavity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Piazza, Francesco, E-mail: francesco.piazza@ph.tum.de; Strack, Philipp; Zwerger, Wilhelm

We provide an exact solution for the interplay between Bose–Einstein condensation and the Dicke–Hepp–Lieb self-organization transition of an ideal Bose gas trapped inside a single-mode optical cavity and subject to a transverse laser drive. Based on an effective action approach, we determine the full phase diagram at arbitrary temperature, which features a bi-critical point where the transitions cross. We calculate the dynamically generated band structure of the atoms and the associated suppression of the critical temperature for Bose–Einstein condensation in the phase with a spontaneous periodic density modulation. Moreover, we determine the evolution of the polariton spectrum due to themore » coupling of the cavity photons and the atomic field near the self-organization transition, which is quite different above or below the Bose–Einstein condensation temperature. At low temperatures, the critical value of the Dicke–Hepp–Lieb transition decreases with temperature and thus thermal fluctuations can enhance the tendency to a periodic arrangement of the atoms. -- Highlights: •Atoms inside a driven cavity can undergo two transitions: self-organization and BEC. •The phase diagram has four phases which coexist at a bi-critical point. •Atom–cavity coupling creates a dynamical lattice for the atoms. •Finite temperature can enhance the tendency towards self-organization. •We calculate the detailed spectrum of the polaritonic excitations.« less

Vanishing amplitude of backbone dynamics causes a true protein dynamical transition: H2 NMR studies on perdeuterated C-phycocyanin

NASA Astrophysics Data System (ADS)

Kämpf, Kerstin; Kremmling, Beke; Vogel, Michael

2014-03-01

Using a combination of H2 nuclear magnetic resonance (NMR) methods, we study internal rotational dynamics of the perdeuterated protein C-phycocyanin (CPC) in dry and hydrated states over broad temperature and dynamic ranges with high angular resolution. Separating H2 NMR signals from methyl deuterons, we show that basically all backbone deuterons exhibit highly restricted motion occurring on time scales faster than microseconds. The amplitude of this motion increases when a hydration shell exists, while it decreases upon cooling and vanishes near 175 K. We conclude that the vanishing of the highly restricted motion marks a dynamical transition, which is independent of the time window and of a fundamental importance. This conclusion is supported by results from experimental and computational studies of the proteins myoglobin and elastin. In particular, we argue based on findings in molecular dynamics simulations that the behavior of the highly restricted motion of proteins at the dynamical transition resembles that of a characteristic secondary relaxation of liquids at the glass transition, namely the nearly constant loss. Furthermore, H2 NMR studies on perdeuterated CPC reveal that, in addition to highly restricted motion, small fractions of backbone segments exhibit weakly restricted dynamics when temperature and hydration are sufficiently high.

Experimental evidence of a liquid-liquid transition in interfacial water

NASA Astrophysics Data System (ADS)

Zanotti, J.-M.; Bellissent-Funel, M.-C.; Chen, S.-H.

2005-07-01

At ambient pressure, bulk liquid water shows an anomalous increase of thermodynamic quantities and apparent divergences of dynamic properties on approaching a temperature Ts of 228 K. At normal pressure, supercooled water spontaneously freezes below the homogeneous nucleation temperature, TH = 235 K. Upon heating, the two forms of Amorphous Solid Water (ASW), LDA (Low Density Amorphous Ice) and HDA (High Density Amorphous Ice), crystallise above TX = 150 K. As a consequence, up to now no experiment has been able to explore the properties of liquid water in this very interesting temperature range between 150 and 235 K. We present nanosecond-time-scale measurements of local rotational and translational dynamics of interfacial, non-crystalline, water from 77 to 280 K. These experimental dynamic results are combined with calorimetric and diffraction data to show that after exhibiting a glass transition at 165 K, interfacial water experiences a first-order liquid-liquid transition at 240 K from a low-density to a high-density liquid. This is the first direct evidence of the existence of a liquid-liquid transition involving water.

Quasi-dynamic pressure and temperature initiated β<-->δ solid phase transitions in HMX

NASA Astrophysics Data System (ADS)

Zaug, Joseph M.; Farber, Daniel L.; Craig, Ian M.; Blosch, Laura L.; Shuh, David K.; Hansen, Donald W.; Aracne-Ruddle, Chantel M.

2000-04-01

The phase transformation of β-HMX (>0.5% RDX) to δ phase has been studied for over twenty years and more recently with an high-contrast optical second harmonic generation technique. Shock studies of the plastic binder composites of HMX have indicated that the transition is perhaps irreversible, a result that concurs with the static pressure results published by F. Goetz et al. [1] in 1978. However, the stability field favors the β polymorph over δ as pressure is increased (up to 5.4 GPa) along any thermodynamically reasonable isotherm. In this experiment, strict control of pressure and temperature is maintained while x-ray and optical diagnostics are applied to monitor the conformational dynamics of HMX. Unlike the temperature induced β→δ transition, the pressure induced is heterogeneous in nature. The 1 bar 25 °C δ→β transition is not immediate, occuring over tens of hours. Transition points and kinetics are path dependent and consequently this paper describes our work in progress.

Twinning to slip transition in ultrathin BCC Fe nanowires

NASA Astrophysics Data System (ADS)

Sainath, G.; Choudhary, B. K.

2018-04-01

We report twinning to slip transition with decreasing size and increasing temperature in ultrathin <100> BCC Fe nanowires. Molecular dynamics simulations have been performed on different nanowire size in the range 0.404-3.634 nm at temperatures ranging from 10 to 900 K. The results indicate that slip mode dominates at low sizes and high temperatures, while deformation twinning is promoted at high sizes and low temperatures. The temperature, at which the nanowires show twinning to slip transition, increases with increasing size. The different modes of deformation are also reflected appropriately in the respective stress-strain behaviour of the nanowires.

Molecular dynamics study of melting and fcc-bcc transitions in Xe.

PubMed

Belonoshko, A B; Ahuja, R; Johansson, B

2001-10-15

We have investigated the phase diagram of Xe over a wide pressure-temperature range by molecular dynamics. The calculated melting curve is in good agreement with earlier experimental data. At a pressure of around 25 GPa and a temperature of about 2700 K we find a triple fcc-bcc liquid point. The calculated fcc-bcc boundary is in nice agreement with the experimental points, which, however, were interpreted as melting. This finding suggests that the transition from close-packed to bcc structure might be more common at high pressure and high temperature than was previously anticipated.

Dynamic thermal expansivity of liquids near the glass transition.

PubMed

Niss, Kristine; Gundermann, Ditte; Christensen, Tage; Dyre, Jeppe C

2012-04-01

Based on previous works on polymers by Bauer et al. [Phys. Rev. E 61, 1755 (2000)], this paper describes a capacitative method for measuring the dynamical expansion coefficient of a viscous liquid. Data are presented for the glass-forming liquid tetramethyl tetraphenyl trisiloxane (DC704) in the ultraviscous regime. Compared to the method of Bauer et al., the dynamical range has been extended by making time-domain experiments and by making very small and fast temperature steps. The modeling of the experiment presented in this paper includes the situation in which the capacitor is not full because the liquid contracts when cooling from room temperature down to around the glass-transition temperature, which is relevant when measuring on a molecular liquid rather than a polymer.

Bifurcation Theory of the Transition to Collisionless Ion-temperature-gradient-driven Plasma Turbulence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kolesnikov, R.A.; Krommes, J.A.

The collisionless limit of the transition to ion-temperature-gradient-driven plasma turbulence is considered with a dynamical-systems approach. The importance of systematic analysis for understanding the differences in the bifurcations and dynamics of linearly damped and undamped systems is emphasized. A model with ten degrees of freedom is studied as a concrete example. A four-dimensional center manifold (CM) is analyzed, and fixed points of its dynamics are identified and used to predict a ''Dimits shift'' of the threshold for turbulence due to the excitation of zonal flows. The exact value of that shift in terms of physical parameters is established for themore » model; the effects of higher-order truncations on the dynamics are noted. Multiple-scale analysis of the CM equations is used to discuss possible effects of modulational instability on scenarios for the transition to turbulence in both collisional and collisionless cases.« less

Predict the glass transition temperature of glycerol-water binary cryoprotectant by molecular dynamic simulation.

PubMed

Li, Dai-Xi; Liu, Bao-Lin; Liu, Yi-shu; Chen, Cheng-lung

2008-04-01

Vitrification is proposed to be the best way for the cryopreservation of organs. The glass transition temperature (T(g)) of vitrification solutions is a critical parameter of fundamental importance for cryopreservation by vitrification. The instruments that can detect the thermodynamic, mechanical and dielectric changes of a substance may be used to determine the glass transition temperature. T(g) is usually measured by using differential scanning calorimetry (DSC). In this study, the T(g) of the glycerol-aqueous solution (60%, wt/%) was determined by isothermal-isobaric molecular dynamic simulation (NPT-MD). The software package Discover in Material Studio with the Polymer Consortium Force Field (PCFF) was used for the simulation. The state parameters of heat capacity at constant pressure (C(p)), density (rho), amorphous cell volume (V(cell)) and specific volume (V(specific)) and radial distribution function (rdf) were obtained by NPT-MD in the temperature range of 90-270K. These parameters showed a discontinuity at a specific temperature in the plot of state parameter versus temperature. The temperature at the discontinuity is taken as the simulated T(g) value for glycerol-water binary solution. The T(g) values determined by simulation method were compared with the values in the literatures. The simulation values of T(g) (160.06-167.51K) agree well with the DSC results (163.60-167.10K) and the DMA results (159.00K). We drew the conclusion that molecular dynamic simulation (MDS) is a potential method for investigating the glass transition temperature (T(g)) of glycerol-water binary cryoprotectants and may be used for other vitrification solutions.

The deconfining phase transition in and out of equilibrium

NASA Astrophysics Data System (ADS)

Bazavov, Oleksiy

Recent experiments carried out at the Relativistic Heavy Ion Collider at the Brookhaven National Laboratory provide strong evidence that a matter can be driven from a confined, low-temperature phase, observed in our every day world into a deconfined high-temperature phase of liberated quarks and gluons. The equilibrium and dynamical properties of the deconfining phase transition are thus of great theoretical interest, since they also provide an information about the first femtoseconds of the evolution of our Universe, when the hot primordial soup while cooling has undergone a chain of phase transitions. The aspects of the deconfining phase transition studied in this work include: the dynamics of the SU(3) gauge theory after the heating quench (which models rapid heating in the heavy-ion collisions), equilibrium properties of the phase transition in the SU(3) gauge theory with boundaries at low temperature (small volumes at RHIC suggest that boundary effects cannot be neglected and periodic boundary conditions normally used in lattice simulations do not correspond to the experimental situation), and a study of the order of the transition in U(1) gauge theory.

Transition in coupled replicas may not imply a finite-temperature ideal glass transition in glass-forming systems.

PubMed

Garrahan, Juan P

2014-03-01

A key open question in the glass transition field is whether a finite temperature thermodynamic transition to the glass state exists or not. Recent simulations of coupled replicas in atomistic models have found signatures of a static transition as a function of replica coupling. This can be viewed as evidence of an associated thermodynamic glass transition in the uncoupled system. We demonstrate here that a different interpretation is possible. We consider the triangular plaquette model, an interacting spin system which displays (East model-like) glassy dynamics in the absence of any static transition. We show that when two replicas are coupled, there is a curve of equilibrium phase transitions, between phases of small and large overlap, in the temperature-coupling plane (located on the self-dual line of an exact temperature-coupling duality of the system) which ends at a critical point. Crucially, in the limit of vanishing coupling the finite temperature transition disappears, and the uncoupled system is in the disordered phase at all temperatures. We discuss an interpretation of atomistic simulations in light of this result.

Electrostatics of the protein-water interface and the dynamical transition in proteins.

PubMed

Matyushov, Dmitry V; Morozov, Alexander Y

2011-07-01

Atomic displacements of hydrated proteins are dominated by phonon vibrations at low temperatures and by dissipative large-amplitude motions at high temperatures. A crossover between the two regimes is known as a dynamical transition. Recent experiments indicate a connection between the dynamical transition and the dielectric response of the hydrated protein. We analyze two mechanisms of the coupling between the protein atomic motions and the protein-water interface. The first mechanism considers viscoelastic changes in the global shape of the protein plasticized by its coupling to the hydration shell. The second mechanism involves modulations of the local motions of partial charges inside the protein by electrostatic fluctuations. The model is used to analyze mean-square displacements of iron of metmyoglobin reported by Mössbauer spectroscopy. We show that high displacement of heme iron at physiological temperatures is dominated by electrostatic fluctuations. Two onsets, one arising from the viscoelastic response and the second from electrostatic fluctuations, are seen in the temperature dependence of the mean-square displacements when the corresponding relaxation times enter the instrumental resolution window.

Electrostatics of the protein-water interface and the dynamical transition in proteins

NASA Astrophysics Data System (ADS)

Matyushov, Dmitry V.; Morozov, Alexander Y.

2011-07-01

Atomic displacements of hydrated proteins are dominated by phonon vibrations at low temperatures and by dissipative large-amplitude motions at high temperatures. A crossover between the two regimes is known as a dynamical transition. Recent experiments indicate a connection between the dynamical transition and the dielectric response of the hydrated protein. We analyze two mechanisms of the coupling between the protein atomic motions and the protein-water interface. The first mechanism considers viscoelastic changes in the global shape of the protein plasticized by its coupling to the hydration shell. The second mechanism involves modulations of the local motions of partial charges inside the protein by electrostatic fluctuations. The model is used to analyze mean-square displacements of iron of metmyoglobin reported by Mössbauer spectroscopy. We show that high displacement of heme iron at physiological temperatures is dominated by electrostatic fluctuations. Two onsets, one arising from the viscoelastic response and the second from electrostatic fluctuations, are seen in the temperature dependence of the mean-square displacements when the corresponding relaxation times enter the instrumental resolution window.

Dynamism or Disorder at High Pressures?

NASA Astrophysics Data System (ADS)

Angel, R. J.; Bismayer, U.; Marshall, W. G.

2002-12-01

Phase transitions in minerals at elevated temperatures typically involve dynamics as a natural consequence of the increase in thermal energy available to the system. Classic examples include quartz, cristobalite, and carbonates in which the high-temperature, high symmetry phase is dynamically disordered. This disorder has important thermodynamic consequences, including displacement and curvature of phase boundaries (e.g. calcite-aragonite). In other minerals such as clinopyroxenes and anorthite feldspar, the dynamic behaviour is restricted to the neighbourhood of the phase transition. The fundamental question is whether increasing pressure generally suppresses such dynamic behaviour (as in anorthite; Angel, 1988), or not. In the latter case it must be included in thermodynamic models of high-pressure phase equilibria and seismological modelling of the mantle; the potential dynamics and softening in stishovite may provide the critical observational constraint on the presence or otherwise of free silica in the lower mantle. We have continued to use the lead phosphate as a prototype ferroelastic in which to understand dynamic behaviour, simply because its dynamics and transition behaviour is far better characterised than any mineral. Furthermore, the phase transition is at a pressure where experimental difficulties do not dominate the experimental results. Our previous neutron diffraction study (Angel et al., 2001) revealed that some disorder, either dynamic or static, is retained in the high-symmetry, high-pressure phase just above the phase transition. New neutron diffraction data on the pure material now suggests that this disorder slowly decreases with increasing pressure until at twice the transition pressure it is ordered. Further data for doped material provides insights into the nature of this disorder. Angel (1988) Amer. Mineral. 73:1114. Angel et al (2001) J PhysC 13: 5353.

Contrasting dynamics of fragile and non-fragile polyalcohols through the glass, and dynamical, transitions: A comparison of neutron scattering and dielectric relaxation data for sorbitol and glycerol.

PubMed

Migliardo, F; Angell, C A; Magazù, S

2017-01-01

Glycerol and sorbitol are glass-forming hydrogen-bonded systems characterized by intriguing properties which make these systems very interesting also from the applications point of view. The goal of this work is to relate the hydrogen-bonded features, relaxation dynamics, glass transition properties and fragility of these systems, in particular to seek insight into their very different liquid fragilities. The comparison between glycerol and sorbitol is carried out by collecting the elastic incoherent neutron scattering (EINS) intensity as a function of temperature and of the instrumental energy resolution. Intensity data vs temperature and resolution are analyzed in terms of thermal restraint and Resolution Elastic Neutron Scattering (RENS) approaches. The number of OH groups, which are related to the connecting sites, is a significant parameter both in the glass transition and in the dynamical transition. On the other hand, the disordered nature of sorbitol is confirmed by the existence of different relaxation processes. From the applications point of view, glycerol and sorbitol have remarkable bioprotectant properties which make these systems useful in different technological and industrial fields. Furthermore, polyols are rich in glassforming liquid phenomenology and highly deserving of study in their own right. The comparison of EINS and calorimetric data on glycerol and sorbitol helps provide a connection between structural relaxation, dynamical transition, glass transition, and fragility. The evaluation of the inflection point in the elastic intensity behavior as a function of temperature and instrumental energy resolution provides a confirmation of the validity of the RENS approach. This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazù and Dr. Federica Migliardo. Copyright © 2016. Published by Elsevier B.V.

Striking role of non-bridging oxygen on glass transition temperature of calcium aluminosilicate glass-formers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bouhadja, M.; Jakse, N.; Pasturel, A.

2014-06-21

Molecular dynamics simulations are used to study the structural and dynamic properties of calcium aluminosilicate, (CaO-Al{sub 2}O{sub 3}){sub 1−x}(SiO{sub 2}){sub x}, glass formers along three joins, namely, R = 1, 1.57, and 3, in which the silica content x can vary from 0 to 1. For all compositions, we determined the glass-transition temperature, the abundances of the non-bridging oxygen, triclusters, and AlO{sub 5} structural units, as well as the fragility from the temperature evolution of the α-relaxation times. We clearly evidence the role played by the non-bridging oxygen linked either to Al atoms or Si atoms in the evolution ofmore » the glass-transition temperature as well as of the fragility as a function of silica content along the three joins.« less

Molecular dynamics simulation of premelting and melting phase transitions in stoichiometric uranium dioxide

NASA Astrophysics Data System (ADS)

Yakub, Eugene; Ronchi, Claudio; Staicu, Dragos

2007-09-01

Results of molecular dynamics (MD) simulation of UO2 in a wide temperature range are presented and discussed. A new approach to the calibration of a partly ionic Busing-Ida-type model is proposed. A potential parameter set is obtained reproducing the experimental density of solid UO2 in a wide range of temperatures. A conventional simulation of the high-temperature stoichiometric UO2 on large MD cells, based on a novel fast method of computation of Coulomb forces, reveals characteristic features of a premelting λ transition at a temperature near to that experimentally observed (Tλ=2670K ). A strong deviation from the Arrhenius behavior of the oxygen self-diffusion coefficient was found in the vicinity of the transition point. Predictions for liquid UO2, based on the same potential parameter set, are in good agreement with existing experimental data and theoretical calculations.

Protein-style dynamical transition in a non-biological polymer and a non-aqueous solvent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mamontov, E.; Sharma, V. K.; Borreguero, J. M.

Using neutron scattering and molecular dynamics simulation, techniques most often associated with protein dynamical transition studies, we have investigated the microscopic dynamics of one of the most common polymers, polystyrene, which was exposed to toluene vapor, mimicking the process of protein hydration from water vapor. Polystyrene with adsorbed toluene is an example of a solvent-solute system, which, unlike biopolymers, is anhydrous and lacks hydrogen bonding. Nevertheless, it exhibits the essential traits of the dynamical transition in biomolecules, such as a specific dependence of the microscopic dynamics of both solvent and host on the temperature and the amount of solvent adsorbed.more » Ultimately, we conclude that the protein dynamical transition is a manifestation of a universal solvent-solute dynamical relationship, which is not specific to either biomolecules as solute, or aqueous media as solvent, or even a particular type of interactions between solvent and solute.« less

Protein-style dynamical transition in a non-biological polymer and a non-aqueous solvent

DOE PAGES

Mamontov, E.; Sharma, V. K.; Borreguero, J. M.; ...

2016-03-15

Using neutron scattering and molecular dynamics simulation, techniques most often associated with protein dynamical transition studies, we have investigated the microscopic dynamics of one of the most common polymers, polystyrene, which was exposed to toluene vapor, mimicking the process of protein hydration from water vapor. Polystyrene with adsorbed toluene is an example of a solvent-solute system, which, unlike biopolymers, is anhydrous and lacks hydrogen bonding. Nevertheless, it exhibits the essential traits of the dynamical transition in biomolecules, such as a specific dependence of the microscopic dynamics of both solvent and host on the temperature and the amount of solvent adsorbed.more » Ultimately, we conclude that the protein dynamical transition is a manifestation of a universal solvent-solute dynamical relationship, which is not specific to either biomolecules as solute, or aqueous media as solvent, or even a particular type of interactions between solvent and solute.« less

New Scenario of Dynamical Heterogeneity in Supercooled Liquid and Glassy States of 2D Monatomic System.

PubMed

Van Hoang, Vo; Teboul, Victor; Odagaki, Takashi

2015-12-24

Via analysis of spatiotemporal arrangements of atoms based on their dynamics in supercooled liquid and glassy states of a 2D monatomic system with a double-well Lennard-Jones-Gauss (LJG) interaction potential, we find a new scenario of dynamical heterogeneity. Atoms with the same or very close mobility have a tendency to aggregate into clusters. The number of atoms with high mobility (and size of their clusters) increases with decreasing temperature passing over a maximum before decreasing down to zero. Position of the peak moves toward a lower temperature if mobility of atoms in clusters is lower together with an enhancement of height of the peak. In contrast, the number of atoms with very low mobility or solidlike atoms (and size of their clusters) has a tendency to increase with decreasing temperature and then it suddenly increases in the vicinity of the glass transition temperature leading to the formation of a glassy state. A sudden increase in the number of strongly correlated solidlike atoms in the vicinity of a glass transition temperature (Tg) may be an origin of a drastical increase in viscosity of the glass-forming systems approaching the glass transition. In fact, we find that the diffusion coefficient decays exponentially with a fraction of solidlike atoms exhibiting a sudden decrease in the vicinity of the glass transition region.

Dynamics of Uncrystallized Water, Ice, and Hydrated Protein in Partially Crystallized Gelatin-Water Mixtures Studied by Broadband Dielectric Spectroscopy.

PubMed

Sasaki, Kaito; Panagopoulou, Anna; Kita, Rio; Shinyashiki, Naoki; Yagihara, Shin; Kyritsis, Apostolos; Pissis, Polycarpos

2017-01-12

The glass transition of partially crystallized gelatin-water mixtures was investigated using broadband dielectric spectroscopy (BDS) over a wide range of frequencies (10 mHz to 10 MHz), temperatures (113-298 K), and concentrations (10-45 wt %). Three dielectric relaxation processes (processes I, II, and III) were clearly observed. Processes I, II, and III originate from uncrystallized water (UCW) in the hydration shells of gelatin, ice, and hydrated gelatin, respectively. A dynamic crossover, called the Arrhenius to non-Arrhenius transition of UCW, was observed at the glass transition temperature of the relaxation process of hydrated gelatin for all mixtures. The amount of UCW increases with increasing gelatin content. However, above 35 wt % gelatin, the amount of UCW became more dependent on the gelatin concentration. This increase in UCW causes a decrease in the glass transition temperature of the cooperative motion of gelatin and UCW, which appears to result from a change in the aggregation structure of gelatin in the mixture at a gelatin concentration of approximately 35 wt %. The temperature dependence of the relaxation time of process II has nearly the same activation energy as pure ice made by slow crystallization of ice Ih. This implies that process II originates from the dynamics of slowly crystallized ice Ih.

Finite-connectivity spin-glass phase diagrams and low-density parity check codes.

PubMed

Migliorini, Gabriele; Saad, David

2006-02-01

We obtain phase diagrams of regular and irregular finite-connectivity spin glasses. Contact is first established between properties of the phase diagram and the performance of low-density parity check (LDPC) codes within the replica symmetric (RS) ansatz. We then study the location of the dynamical and critical transition points of these systems within the one step replica symmetry breaking theory (RSB), extending similar calculations that have been performed in the past for the Bethe spin-glass problem. We observe that the location of the dynamical transition line does change within the RSB theory, in comparison with the results obtained in the RS case. For LDPC decoding of messages transmitted over the binary erasure channel we find, at zero temperature and rate , an RS critical transition point at while the critical RSB transition point is located at , to be compared with the corresponding Shannon bound . For the binary symmetric channel we show that the low temperature reentrant behavior of the dynamical transition line, observed within the RS ansatz, changes its location when the RSB ansatz is employed; the dynamical transition point occurs at higher values of the channel noise. Possible practical implications to improve the performance of the state-of-the-art error correcting codes are discussed.

Finite-density transition line for QCD with 695 MeV dynamical fermions

NASA Astrophysics Data System (ADS)

Greensite, Jeff; Höllwieser, Roman

2018-06-01

We apply the relative weights method to SU(3) gauge theory with staggered fermions of mass 695 MeV at a set of temperatures in the range 151 ≤T ≤267 MeV , to obtain an effective Polyakov line action at each temperature. We then apply a mean field method to search for phase transitions in the effective theory at finite densities. The result is a transition line in the plane of temperature and chemical potential, with an end point at high temperature, as expected, but also a second end point at a lower temperature. We cannot rule out the possibilities that a transition line reappears at temperatures lower than the range investigated, or that the second end point is absent for light quarks.

Dissipative Dynamics of Enzymes

NASA Astrophysics Data System (ADS)

Ariyaratne, Amila; Wu, Chenhao; Tseng, Chiao-Yu; Zocchi, Giovanni

2014-11-01

We explore enzyme conformational dynamics at sub-Å resolution, specifically, temperature effects. The ensemble-averaged mechanical response of the folded enzyme is viscoelastic in the whole temperature range between the warm and cold denaturation transitions. The dissipation parameter γ of the viscoelastic description decreases by a factor of 2 as the temperature is raised from 10 to 45 °C ; the elastic parameter K shows a similar decrease. Thus, when probed dynamically, the enzyme softens for increasing temperature. Equilibrium mechanical experiments with the DNA spring (and a different enzyme) also show, qualitatively, a small softening for increasing temperature.

Dissipative Dynamics of Enzymes

NASA Astrophysics Data System (ADS)

Ariyaratne, Amila; Wu, Chenhao; Tseng, Chiao-Yu; Zocchi, Giovanni; Zocchi LabMolecular Biophysics Team

2015-03-01

We explore enzyme conformational dynamics at sub - Å resolution, specifically temperature effects. The ensemble averaged mechanical response of the folded enzyme is viscoelastic in the whole temperature range between the warm and cold denaturation transitions. The dissipation parameter γ of the viscoelastic description decreases by a factor 2 as the temperature is raised from 10 C to 45 C; the elastic parameter K shows a similar decrease. Thus when probed dynamically, the enzyme softens for increasing temperature. Equilibrium mechanical experiments with the DNA spring (and a different enzyme) also show, qualitatively, a small softening for increasing temperature.

Dissipative dynamics of enzymes.

PubMed

Ariyaratne, Amila; Wu, Chenhao; Tseng, Chiao-Yu; Zocchi, Giovanni

2014-11-07

We explore enzyme conformational dynamics at sub-Å resolution, specifically, temperature effects. The ensemble-averaged mechanical response of the folded enzyme is viscoelastic in the whole temperature range between the warm and cold denaturation transitions. The dissipation parameter γ of the viscoelastic description decreases by a factor of 2 as the temperature is raised from 10 to 45 °C; the elastic parameter K shows a similar decrease. Thus, when probed dynamically, the enzyme softens for increasing temperature. Equilibrium mechanical experiments with the DNA spring (and a different enzyme) also show, qualitatively, a small softening for increasing temperature.

Stability-to-instability transition in the structure of large-scale networks

NASA Astrophysics Data System (ADS)

Hu, Dandan; Ronhovde, Peter; Nussinov, Zohar

2012-12-01

We examine phase transitions between the “easy,” “hard,” and “unsolvable” phases when attempting to identify structure in large complex networks (“community detection”) in the presence of disorder induced by network “noise” (spurious links that obscure structure), heat bath temperature T, and system size N. The partition of a graph into q optimally disjoint subgraphs or “communities” inherently requires Potts-type variables. In earlier work [Philos. Mag.1478-643510.1080/14786435.2011.616547 92, 406 (2012)], when examining power law and other networks (and general associated Potts models), we illustrated that transitions in the computational complexity of the community detection problem typically correspond to spin-glass-type transitions (and transitions to chaotic dynamics in mechanical analogs) at both high and low temperatures and/or noise. The computationally “hard” phase exhibits spin-glass type behavior including memory effects. The region over which the hard phase extends in the noise and temperature phase diagram decreases as N increases while holding the average number of nodes per community fixed. This suggests that in the thermodynamic limit a direct sharp transition may occur between the easy and unsolvable phases. When present, transitions at low temperature or low noise correspond to entropy driven (or “order by disorder”) annealing effects, wherein stability may initially increase as temperature or noise is increased before becoming unsolvable at sufficiently high temperature or noise. Additional transitions between contending viable solutions (such as those at different natural scales) are also possible. Identifying community structure via a dynamical approach where “chaotic-type” transitions were found earlier. The correspondence between the spin-glass-type complexity transitions and transitions into chaos in dynamical analogs might extend to other hard computational problems. In this work, we examine large networks (with a power law distribution in cluster size) that have a large number of communities (q≫1). We infer that large systems at a constant ratio of q to the number of nodes N asymptotically tend towards insolvability in the limit of large N for any positive T. The asymptotic behavior of temperatures below which structure identification might be possible, T×=O[1/lnq], decreases slowly, so for practical system sizes, there remains an accessible, and generally easy, global solvable phase at low temperature. We further employ multivariate Tutte polynomials to show that increasing q emulates increasing T for a general Potts model, leading to a similar stability region at low T. Given the relation between Tutte and Jones polynomials, our results further suggest a link between the above complexity transitions and transitions associated with random knots.

Temperature dependent micro-rheology of a glass-forming polymer melt studied by molecular dynamics simulation.

PubMed

Kuhnhold, A; Paul, W

2014-09-28

We present a Molecular Dynamics simulation study of a micro-rheological probing of the glass transition in a polymer melt. Our model system consists of short bead-spring chains and the temperature ranges from well above the glass transition temperature to about 10% above it. The nano-particle clearly couples to the slowing down of the polymer segments and the calculated storage and loss moduli reveal the approach to the glass transition. At temperatures close to the mode coupling Tc of the polymer melt, the micro-rheological moduli measure the local viscoelastic response of the cage of monomers surrounding the nano-particle and no longer reveal the true melt moduli. The incoherent scattering function of the nano-particle exhibits a stretched exponential decay, typical for the α-process in glass forming systems. We find no indication of a strong superdiffusive regime as has been deduced from a recent experiment in the same temperature range but for smaller momentum transfers.

Enhanced power factor via the control of structural phase transition in SnSe

PubMed Central

Yu, Hulei; Dai, Shuai; Chen, Yue

2016-01-01

Tin selenide has attracted much research interest due to its unprecedentedly high thermoelectric figure of merit (ZT). For real applications, it is desirable to increase the ZT value in the lower-temperature range, as the peak ZT value currently exists near the melting point. It is shown in this paper that the structural phase transition plays an important role in boosting the ZT value of SnSe in the lower-temperature range, as the Cmcm phase is found to have a much higher power factor than the Pnma phase. Furthermore, hydrostatic pressure is predicted to be extremely effective in tuning the phase transition temperature based on ab-initio molecular dynamic simulations; a remarkable decrease in the phase transition temperature is found when a hydrostatic pressure is applied. Dynamical stabilities are investigated based on phonon calculations, providing deeper insight into the pressure effects. Accurate band structures are obtained using the modified Becke-Johnson correction, allowing reliable prediction of the electrical transport properties. The effects of hydrostatic pressure on the thermal transport properties are also discussed. Hydrostatic pressure is shown to be efficient in manipulating the transport properties via the control of phase transition temperature in SnSe, paving a new path for enhancing its thermoelectric efficiency. PMID:27193260

Local dynamics of glass-forming polystyrene thin films from atomistic simulation

NASA Astrophysics Data System (ADS)

Zhou, Yuxing; Milner, Scott

Despite a wide technological application ranging from protective coatings to organic solar cells, there still no consensus on the mechanism for the glass transition in polymer thin films a manifestation of the infamous glass problem under confinement. Many experimental and computational studies have observed a large deviation of nanoscale dynamical properties in thin films from the corresponding properties in bulk. In this work, we perform extensive united-atom simulations on atactic polystyrene free-standing thin films near the glass transition temperature and focus on the effect of free surface on the local dynamics. We study the segmental dynamics as a function of distance from the surface for different temperatures, from which relaxation time and thereby local Tg is obtained for each layer. We find the dynamics near free surface is not only enhanced but becomes less strongly temperature dependent as Tg is approached compared to the bulk. We find an increasing length scale associated with mobility propagation from the free surface as temperature decreases, but no correlation between local structure and enhanced relaxation rates near the surface, consistent with studies on bead-spring chains.

Analysis of the anomalous mean-field like properties of Gaussian core model in terms of entropy

NASA Astrophysics Data System (ADS)

Nandi, Manoj Kumar; Maitra Bhattacharyya, Sarika

2018-01-01

Studies of the Gaussian core model (GCM) have shown that it behaves like a mean-field model and the properties are quite different from standard glass former. In this work, we investigate the entropies, namely, the excess entropy (Sex) and the configurational entropy (Sc) and their different components to address these anomalies. Our study corroborates most of the earlier observations and also sheds new light on the high and low temperature dynamics. We find that unlike in standard glass former where high temperature dynamics is dominated by two-body correlation and low temperature by many-body correlations, in the GCM both high and low temperature dynamics are dominated by many-body correlations. We also find that the many-body entropy which is usually positive at low temperatures and is associated with activated dynamics is negative in the GCM suggesting suppression of activation. Interestingly despite the suppression of activation, the Adam-Gibbs (AG) relation that describes activated dynamics holds in the GCM, thus suggesting a non-activated contribution in AG relation. We also find an overlap between the AG relation and mode coupling power law regime leading to a power law behavior of Sc. From our analysis of this power law behavior, we predict that in the GCM the high temperature dynamics will disappear at dynamical transition temperature and below that there will be a transition to the activated regime. Our study further reveals that the activated regime in the GCM is quite narrow.

Enhanced sampling simulation analysis of the structure of lignin in the THF–water miscibility gap

DOE PAGES

Smith, Micholas Dean; Petridis, Loukas; Cheng, Xiaolin; ...

2016-01-26

Using temperature replica-exchange molecular dynamics, we characterize a globule-to-coil transition for a softwood-like lignin biopolymer in a tetrahydrofuran (THF)-water cosolvent system at temperatures at which the cosolvent undergoes a de-mixing transition. The lignin is found to be in a coil state, similar to that in the high-temperature miscible region. Analysis of the transition kinetics indicates that THF acts in a surfactant-like fashion. In conclusion, the present study thus suggests that THF-water based pretreatments may efficiently remove lignin from biomass even at relatively low (non-water boiling) temperatures.

Relaxation mechanisms in glassy dynamics: the Arrhenius and fragile regimes.

PubMed

Hentschel, H George E; Karmakar, Smarajit; Procaccia, Itamar; Zylberg, Jacques

2012-06-01

Generic glass formers exhibit at least two characteristic changes in their relaxation behavior, first to an Arrhenius-type relaxation at some characteristic temperature and then at a lower characteristic temperature to a super-Arrhenius (fragile) behavior. We address these transitions by studying the statistics of free energy barriers for different systems at different temperatures and space dimensions. We present a clear evidence for changes in the dynamical behavior at the transition to Arrhenius and then to a super-Arrhenius behavior. A simple model is presented, based on the idea of competition between single-particle and cooperative dynamics. We argue that Arrhenius behavior can take place as long as there is enough free volume for the completion of a simple T1 relaxation process. Once free volume is absent one needs a cooperative mechanism to "collect" enough free volume. We show that this model captures all the qualitative behavior observed in simulations throughout the considered temperature range.

Reorientational dynamics in molecular liquids as revealed by dynamic light scattering: from boiling point to glass transition temperature.

PubMed

Schmidtke, B; Petzold, N; Kahlau, R; Rössler, E A

2013-08-28

We determine the reorientational correlation time τ of a series of molecular liquids by performing depolarized light scattering experiments (double monochromator, Fabry-Perot interferometry, and photon correlation spectroscopy). Correlation times in the range 10(-12) s-100 s are compiled, i.e., the full temperature interval between the boiling point and the glass transition temperature T(g) is covered. We focus on low-T(g) liquids for which the high-temperature limit τ ≅ 10(-12) s is easily accessed by standard spectroscopic equipment (up to 440 K). Regarding the temperature dependence three interpolation formulae of τ(T) with three parameters each are tested: (i) Vogel-Fulcher-Tammann equation, (ii) the approach recently discussed by Mauro et al. [Proc. Natl. Acad. Sci. U.S.A. 106, 19780 (2009)], and (iii) our approach decomposing the activation energy E(T) in a constant high temperature value E∞ and a "cooperative part" E(coop)(T) depending exponentially on temperature [Schmidtke et al., Phys. Rev. E 86, 041507 (2012)]. On the basis of the present data, approaches (i) and (ii) are insufficient as they do not provide the correct crossover to the high-temperature Arrhenius law clearly identified in the experimental data while approach (iii) reproduces the salient features of τ(T). It allows to discuss the temperature dependence of the liquid's dynamics in terms of a E(coop)(T)/E∞ vs. T/E∞ plot and suggests that E∞ controls the energy scale of the glass transition phenomenon.

Speculation and replication in temperature accelerated dynamics

DOE PAGES

Zamora, Richard J.; Perez, Danny; Voter, Arthur F.

2018-02-12

Accelerated Molecular Dynamics (AMD) is a class of MD-based algorithms for the long-time scale simulation of atomistic systems that are characterized by rare-event transitions. Temperature-Accelerated Dynamics (TAD), a traditional AMD approach, hastens state-to-state transitions by performing MD at an elevated temperature. Recently, Speculatively-Parallel TAD (SpecTAD) was introduced, allowing the TAD procedure to exploit parallel computing systems by concurrently executing in a dynamically generated list of speculative future states. Although speculation can be very powerful, it is not always the most efficient use of parallel resources. In this paper, we compare the performance of speculative parallelism with a replica-based technique, similarmore » to the Parallel Replica Dynamics method. A hybrid SpecTAD approach is also presented, in which each speculation process is further accelerated by a local set of replicas. Finally and overall, this work motivates the use of hybrid parallelism whenever possible, as some combination of speculation and replication is typically most efficient.« less

Speculation and replication in temperature accelerated dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zamora, Richard J.; Perez, Danny; Voter, Arthur F.

Accelerated Molecular Dynamics (AMD) is a class of MD-based algorithms for the long-time scale simulation of atomistic systems that are characterized by rare-event transitions. Temperature-Accelerated Dynamics (TAD), a traditional AMD approach, hastens state-to-state transitions by performing MD at an elevated temperature. Recently, Speculatively-Parallel TAD (SpecTAD) was introduced, allowing the TAD procedure to exploit parallel computing systems by concurrently executing in a dynamically generated list of speculative future states. Although speculation can be very powerful, it is not always the most efficient use of parallel resources. In this paper, we compare the performance of speculative parallelism with a replica-based technique, similarmore » to the Parallel Replica Dynamics method. A hybrid SpecTAD approach is also presented, in which each speculation process is further accelerated by a local set of replicas. Finally and overall, this work motivates the use of hybrid parallelism whenever possible, as some combination of speculation and replication is typically most efficient.« less

Financial Symmetry and Moods in the Market

PubMed Central

Savona, Roberto; Soumare, Maxence; Andersen, Jørgen Vitting

2015-01-01

This paper studies how certain speculative transitions in financial markets can be ascribed to a symmetry break that happens in the collective decision making. Investors are assumed to be bounded rational, using a limited set of information including past price history and expectation on future dividends. Investment strategies are dynamically changed based on realized returns within a game theoretical scheme with Nash equilibria. In such a setting, markets behave as complex systems whose payoff reflect an intrinsic financial symmetry that guarantees equilibrium in price dynamics (fundamentalist state) until the symmetry is broken leading to bubble or anti-bubble scenarios (speculative state). We model such two-phase transition in a micro-to-macro scheme through a Ginzburg-Landau-based power expansion leading to a market temperature parameter which modulates the state transitions in the market. Via simulations we prove that transitions in the market price dynamics can be phenomenologically explained by the number of traders, the number of strategies and amount of information used by agents, all included in our market temperature parameter. PMID:25856392

On the nature of a glassy state of matter in a hydrated protein: Relation to protein function.

PubMed

Teeter, M M; Yamano, A; Stec, B; Mohanty, U

2001-09-25

Diverse biochemical and biophysical experiments indicate that all proteins, regardless of size or origin, undergo a dynamic transition near 200 K. The cause of this shift in dynamic behavior, termed a "glass transition," and its relation to protein function are important open questions. One explanation postulated for the transition is solidification of correlated motions in proteins below the transition. We verified this conjecture by showing that crambin's radius of gyration (Rg) remains constant below approximately 180 K. We show that both atom position and dynamics of protein and solvent are physically coupled, leading to a novel cooperative state. This glassy state is identified by negative slopes of the Debye-Waller (B) factor vs. temperature. It is composed of multisubstate side chains and solvent. Based on generalization of Adam-Gibbs' notion of a cooperatively rearranging region and decrease of the total entropy with temperature, we calculate the slope of the Debye-Waller factor. The results are in accord with experiment.

Financial symmetry and moods in the market.

PubMed

Savona, Roberto; Soumare, Maxence; Andersen, Jørgen Vitting

2015-01-01

This paper studies how certain speculative transitions in financial markets can be ascribed to a symmetry break that happens in the collective decision making. Investors are assumed to be bounded rational, using a limited set of information including past price history and expectation on future dividends. Investment strategies are dynamically changed based on realized returns within a game theoretical scheme with Nash equilibria. In such a setting, markets behave as complex systems whose payoff reflect an intrinsic financial symmetry that guarantees equilibrium in price dynamics (fundamentalist state) until the symmetry is broken leading to bubble or anti-bubble scenarios (speculative state). We model such two-phase transition in a micro-to-macro scheme through a Ginzburg-Landau-based power expansion leading to a market temperature parameter which modulates the state transitions in the market. Via simulations we prove that transitions in the market price dynamics can be phenomenologically explained by the number of traders, the number of strategies and amount of information used by agents, all included in our market temperature parameter.

Locally adaptive parallel temperature accelerated dynamics method

NASA Astrophysics Data System (ADS)

Shim, Yunsic; Amar, Jacques G.

2010-03-01

The recently-developed temperature-accelerated dynamics (TAD) method [M. Sørensen and A.F. Voter, J. Chem. Phys. 112, 9599 (2000)] along with the more recently developed parallel TAD (parTAD) method [Y. Shim et al, Phys. Rev. B 76, 205439 (2007)] allow one to carry out non-equilibrium simulations over extended time and length scales. The basic idea behind TAD is to speed up transitions by carrying out a high-temperature MD simulation and then use the resulting information to obtain event times at the desired low temperature. In a typical implementation, a fixed high temperature Thigh is used. However, in general one expects that for each configuration there exists an optimal value of Thigh which depends on the particular transition pathways and activation energies for that configuration. Here we present a locally adaptive high-temperature TAD method in which instead of using a fixed Thigh the high temperature is dynamically adjusted in order to maximize simulation efficiency. Preliminary results of the performance obtained from parTAD simulations of Cu/Cu(100) growth using the locally adaptive Thigh method will also be presented.

Direct comparison of elastic incoherent neutron scattering experiments with molecular dynamics simulations of DMPC phase transitions.

PubMed

Aoun, Bachir; Pellegrini, Eric; Trapp, Marcus; Natali, Francesca; Cantù, Laura; Brocca, Paola; Gerelli, Yuri; Demé, Bruno; Marek Koza, Michael; Johnson, Mark; Peters, Judith

2016-04-01

Neutron scattering techniques have been employed to investigate 1,2-dimyristoyl-sn -glycero-3-phosphocholine (DMPC) membranes in the form of multilamellar vesicles (MLVs) and deposited, stacked multilamellar-bilayers (MLBs), covering transitions from the gel to the liquid phase. Neutron diffraction was used to characterise the samples in terms of transition temperatures, whereas elastic incoherent neutron scattering (EINS) demonstrates that the dynamics on the sub-macromolecular length-scale and pico- to nano-second time-scale are correlated with the structural transitions through a discontinuity in the observed elastic intensities and the derived mean square displacements. Molecular dynamics simulations have been performed in parallel focussing on the length-, time- and temperature-scales of the neutron experiments. They correctly reproduce the structural features of the main gel-liquid phase transition. Particular emphasis is placed on the dynamical amplitudes derived from experiment and simulations. Two methods are used to analyse the experimental data and mean square displacements. They agree within a factor of 2 irrespective of the probed time-scale, i.e. the instrument utilized. Mean square displacements computed from simulations show a comparable level of agreement with the experimental values, albeit, the best match with the two methods varies for the two instruments. Consequently, experiments and simulations together give a consistent picture of the structural and dynamical aspects of the main lipid transition and provide a basis for future, theoretical modelling of dynamics and phase behaviour in membranes. The need for more detailed analytical models is pointed out by the remaining variation of the dynamical amplitudes derived in two different ways from experiments on the one hand and simulations on the other.

Ab Initio Simulations of Temperature Dependent Phase Stability and Martensitic Transitions in NiTi

NASA Technical Reports Server (NTRS)

Haskins, Justin B.; Thompson, Alexander E.; Lawson, John W.

2016-01-01

For NiTi based alloys, the shape memory effect is governed by a transition from a low-temperature martensite phase to a high-temperature austenite phase. Despite considerable experimental and computational work, basic questions regarding the stability of the phases and the martensitic phase transition remain unclear even for the simple case of binary, equiatomic NiTi. We perform ab initio molecular dynamics simulations to describe the temperature-dependent behavior of NiTi and resolve several of these outstanding issues. Structural correlation functions and finite temperature phonon spectra are evaluated to determine phase stability. In particular, we show that finite temperature, entropic effects stabilize the experimentally observed martensite (B19') and austenite (B2) phases while destabilizing the theoretically predicted (B33) phase. Free energy computations based on ab initio thermodynamic integration confirm these results and permit estimates of the transition temperature between the phases. In addition to the martensitic phase transition, we predict a new transition between the B33 and B19' phases. The role of defects in suppressing these phase transformations is discussed.

From boiling point to glass transition temperature: transport coefficients in molecular liquids follow three-parameter scaling.

PubMed

Schmidtke, B; Petzold, N; Kahlau, R; Hofmann, M; Rössler, E A

2012-10-01

The phenomenon of the glass transition is an unresolved problem in condensed matter physics. Its prominent feature, the super-Arrhenius temperature dependence of the transport coefficients, remains a challenge to be described over the full temperature range. For a series of molecular glass formers, we combined τ(T) collected from dielectric spectroscopy and dynamic light scattering covering a range 10(-12) s < τ(T) < 10(2) s. Describing the dynamics in terms of an activation energy E(T), we distinguish a high-temperature regime characterized by an Arrhenius law with a constant activation energy E(∞) and a low-temperature regime for which E(coop)(T) ≡ E(T)-E(∞) increases exponentially while cooling. A scaling is introduced, specifically E(coop)(T)/E(∞) [proportionality] exp[-λ(T/T(A)-1)], where λ is a fragility parameter and T(A) a reference temperature proportional to E(∞). In order to describe τ(T) still the attempt time τ(∞) has to be specified. Thus, a single interaction parameter E(∞) describing the high-temperature regime together with λ controls the temperature dependence of low-temperature cooperative dynamics.

Evaluation of glass transition temperature and dynamic mechanical properties of autopolymerized hard direct denture reline resins.

PubMed

Takase, Kazuma; Watanabe, Ikuya; Kurogi, Tadafumi; Murata, Hiroshi

2015-01-01

This study assessed methods for evaluation of glass transition temperature (Tg) of autopolymerized hard direct denture reline resins using dynamic mechanical analysis and differential scanning calorimetry in addition to the dynamic mechanical properties. The Tg values of 3 different reline resins were determined using a dynamic viscoelastometer and differential scanning calorimeter, and rheological parameters were also determined. Although all materials exhibited higher storage modulus and loss modulus values, and a lower loss tangent at 37˚C with a higher frequency, the frequency dependence was not large. Tg values obtained by dynamic mechanical analysis were higher than those by differential scanning calorimetry and higher frequency led to higher Tg, while more stable Tg values were also obtained by that method. These results suggest that dynamic mechanical analysis is more advantageous for characterization of autopolymerized hard direct denture reline resins than differential scanning calorimetry.

From elemental tellurium to Ge2Sb2Te5 melts: High temperature dynamic and relaxation properties in relationship with the possible fragile to strong transition

NASA Astrophysics Data System (ADS)

Flores-Ruiz, H.; Micoulaut, M.

2018-01-01

We investigate the dynamic properties of Ge-Sb-Te phase change melts using first principles molecular dynamics with a special emphasis on the effect of tellurium composition on melt dynamics. From structural models and trajectories established previously [H. Flores-Ruiz et al., Phys. Rev. B 92, 134205 (2015)], we calculate the diffusion coefficients for the different species, the activation energies for diffusion, the Van Hove correlation, and the intermediate scattering functions able to substantiate the dynamics and relaxation behavior of the liquids as a function of temperature and composition that is also compared to experiment whenever possible. We find that the diffusion is mostly Arrhenius-like and that the addition of Ge/Sb atoms leads to a global decrease of the jump probability and to an increase in activated dynamics for diffusion. Relaxation behavior is analyzed and used in order to evaluate the possibility of a fragile to strong transition that is evidenced from the calculated high fragility (M = 129) of Ge2Sb2Te5 at high temperatures.

Scaling universality at the dynamic vortex Mott transition

DOE PAGES

Lankhorst, M.; Poccia, N.; Stehno, M. P.; ...

2018-01-17

The cleanest way to observe a dynamic Mott insulator-to-metal transition (DMT) without the interference from disorder and other effects inherent to electronic and atomic systems, is to employ the vortex Mott states formed by superconducting vortices in a regular array of pinning sites. Here, we report the critical behavior of the vortex system as it crosses the DMT line, driven by either current or temperature. We find universal scaling with respect to both, expressed by the same scaling function and characterized by a single critical exponent coinciding with the exponent for the thermodynamic Mott transition. We develop a theory formore » the DMT based on the parity reflection-time reversal (PT) symmetry breaking formalism and find that the nonequilibrium-induced Mott transition has the same critical behavior as the thermal Mott transition. Our findings demonstrate the existence of physical systems in which the effect of a nonequilibrium drive is to generate an effective temperature and hence the transition belonging in the thermal universality class.« less

Scaling universality at the dynamic vortex Mott transition

NASA Astrophysics Data System (ADS)

Lankhorst, M.; Poccia, N.; Stehno, M. P.; Galda, A.; Barman, H.; Coneri, F.; Hilgenkamp, H.; Brinkman, A.; Golubov, A. A.; Tripathi, V.; Baturina, T. I.; Vinokur, V. M.

2018-01-01

The cleanest way to observe a dynamic Mott insulator-to-metal transition (DMT) without the interference from disorder and other effects inherent to electronic and atomic systems, is to employ the vortex Mott states formed by superconducting vortices in a regular array of pinning sites. Here, we report the critical behavior of the vortex system as it crosses the DMT line, driven by either current or temperature. We find universal scaling with respect to both, expressed by the same scaling function and characterized by a single critical exponent coinciding with the exponent for the thermodynamic Mott transition. We develop a theory for the DMT based on the parity reflection-time reversal (P T ) symmetry breaking formalism and find that the nonequilibrium-induced Mott transition has the same critical behavior as the thermal Mott transition. Our findings demonstrate the existence of physical systems in which the effect of a nonequilibrium drive is to generate an effective temperature and hence the transition belonging in the thermal universality class.

Dynamic metastability in the two-dimensional Potts ferromagnet

NASA Astrophysics Data System (ADS)

Ibáñez Berganza, Miguel; Petri, Alberto; Coletti, Pietro

2014-05-01

We investigate the nonequilibrium dynamics of the two-dimensional (2D) Potts model on the square lattice after a quench below the discontinuous transition point. By means of numerical simulations of systems with q =12, 24, and 48, we observe the onset of a stationary regime below the temperature-driven transition, in a temperature interval decreasing with the system size and increasing with q. These results obtained dynamically agree with those obtained from the analytical continuation of the free energy [J. L. Meunier and A. Morel, Eur. Phys. J. B 13, 341 (2000), 10.1007/s100510050040], from which metastability in the 2D Potts model results to be a finite-size effect.

Breaking Through the Glass Ceiling: Recent Experimental Approaches to Probe the Properties of Supercooled Liquids near the Glass Transition.

PubMed

Smith, R Scott; Kay, Bruce D

2012-03-15

Experimental measurements of the properties of supercooled liquids at temperatures near their glass transition temperatures, Tg, are requisite for understanding the behavior of glasses and amorphous solids. Unfortunately, many supercooled molecular liquids rapidly crystallize at temperatures far above their Tg, making such measurements difficult to nearly impossible. In this Perspective, we discuss some recent alternative approaches to obtain experimental data in the temperature regime near Tg. These new approaches may yield the additional experimental data necessary to test current theoretical models of the dynamical slowdown that occurs in supercooled liquids approaching the glass transition.

Shock driven melting and resolidification upon release in cerium

NASA Astrophysics Data System (ADS)

Bolme, Cindy; Bronkhorst, Curt; Brown, Don; Cherne, Frank; Cooley, Jason; Furlanetto, Michael; Gleason, Arianna; Jensen, Brian; Owens, Charles; Ali, Suzanne; Fratanduono, Dayne; Galtier, Eric; Granados, Eduardo; Lee, Hae Ja; Nagler, Bob

2017-06-01

The temperature rise due to increasing entropy during shock compression and the corresponding temperature decrease due to isentropic expansion upon release cause the physics of melting and solidification under dynamic pressure changes to differ fundamentally from the more common liquid-solid transitions governed by thermal diffusion. We investigated laser shock driven melting and resolidification during release in cerium to examine the dynamics of these processes. Cerium was selected as the material of study due to the low pressure at which γ-cerium melts along the principle Hugoniot and due to cerium's anomalous melt boundary at low pressure, which facilitates its transition from liquid to solid during isentropic release. The structural phase of cerium was probed with X-ray diffraction using the LCLS X-ray free electron laser, which provided in situ measurements of the transition dynamics. The experimental results will be presented showing the resolidification occurring over 10s of ns.

Elasticity and magnetocaloric effect in MnFe 4Si 3

DOE PAGES

Herlitschke, Marcus; Klobes, B.; Sergueev, I.; ...

2016-03-16

The room temperature magnetocaloric material MnFe 4Si 3 was investigated with nuclear inelastic scattering (NIS) and resonant ultrasound spectroscopy (RUS) at different temperatures and applied magnetic fields in order to assess the infuence of the magnetic transition and the magnetocaloric effect on the lattice dynamics. The NIS data give access to phonons with energies above 3 meV, whereas RUS probes the elasticity of the material in the MHz frequency range and thus low energy, ~5 neV, phonon modes. A significant infuence of the magnetic transition on the lattice dynamics is observed only in the low energy region. Here, MnFe 4Simore » 3 and other compounds in the Mn 5-xFe xSi 3 series were also investigated with vibrating sample magnetometry, resistivity measurements and Moessbauer spectroscopy in order to study the magnetic transitions and to complement the obtained results on the lattice dynamics.« less

Second-order quadrupolar line shapes under molecular dynamics: An additional transition in the extremely fast regime.

PubMed

Hung, Ivan; Wu, Gang; Gan, Zhehong

NMR spectroscopy is a powerful tool for probing molecular dynamics. For the classic case of two-site exchange, NMR spectra go through the transition from exchange broadening through coalescence and then motional narrowing as the exchange rate increases passing through the difference between the resonance frequencies of the two sites. For central-transition spectra of half-integer quadrupolar nuclei in solids, line shape change due to molecular dynamics occurs in two stages. The first stage occurs when the exchange rate is comparable to the second-order quadrupolar interaction. The second spectral transition comes at a faster exchange rate which approaches the Larmor frequency and generally reduces the isotropic quadrupolar shift. Such a two-stage transition phenomenon is unique to half-integer quadrupolar nuclei. A quantum mechanical formalism in full Liouville space is presented to explain the physical origin of the two-stage phenomenon and for use in spectral simulations. Variable-temperature 17 O NMR of solid NaNO 3 in which the NO 3 - ion undergoes 3-fold jumps confirms the two-stage transition process. The spectra of NaNO 3 acquired in the temperature range of 173-413K agree well with simulations using the quantum mechanical formalism. The rate constants for the 3-fold NO 3 - ion jumps span eight orders of magnitude (10 2 -10 10 s -1 ) covering both transitions of the dynamic 17 O line shape. Copyright © 2016 Elsevier Inc. All rights reserved.

Unusual Thermoelectric Behavior Indicating a Hopping to Bandlike Transport Transition in Pentacene

NASA Astrophysics Data System (ADS)

Germs, W. Chr.; Guo, K.; Janssen, R. A. J.; Kemerink, M.

2012-07-01

An unusual increase in the Seebeck coefficient with increasing charge carrier density is observed in pentacene thin film transistors. This behavior is interpreted as being due to a transition from hopping transport in static localized states to bandlike transport, occurring at temperatures below ˜250K. Such a transition can be expected for organic materials in which both static energetic disorder and dynamic positional disorder are important. While clearly visible in the temperature and density dependent Seebeck coefficient, the transition hardly shows up in the charge carrier mobility.

Diffusion-Controlled Recrystallization of Water Sorbed into Poly(meth)acrylates Revealed by Variable-Temperature Mid-Infrared Spectroscopy and Molecular Dynamics Simulation.

PubMed

Yasoshima, Nobuhiro; Fukuoka, Mizuki; Kitano, Hiromi; Kagaya, Shigehiro; Ishiyama, Tatsuya; Gemmei-Ide, Makoto

2017-05-18

Recrystallization behaviors of water sorbed into four poly(meth)acrylates, poly(2-methoxyethyl acrylate), poly(tetrahydrofurfuryl acrylate), poly(methyl acrylate), and poly(methyl methacrylate), are investigated by variable-temperature mid-infrared (VT-MIR) spectroscopy and molecular dynamics (MD) simulation. VT-MIR spectra demonstrate that recrystallization temperatures of water sorbed into the polymers are positively correlated with their glass-transition temperatures reported previously. The present MD simulation shows that a lower-limit temperature of the diffusion for the sorbed water and the glass-transition temperatures of the polymers also have a positive correlation, indicating that the recrystallization is controlled by diffusion mechanism rather than reorientation mechanism. Detailed molecular processes of not only recrystallization during rewarming but also crystallization during cooling and hydrogen-bonding states of water in the polymers are systematically analyzed and discussed.

On the molecular origin of the cooperative coil-to-globule transition of poly(N-isopropylacrylamide) in water.

PubMed

Tavagnacco, L; Zaccarelli, E; Chiessi, E

2018-04-18

By means of atomistic molecular dynamics simulations we investigate the behaviour of poly(N-isopropylacrylamide), PNIPAM, in water at temperatures below and above the lower critical solution temperature (LCST), including the undercooled regime. The transition between water soluble and insoluble states at the LCST is described as a cooperative process involving an intramolecular coil-to-globule transition preceding the aggregation of chains and the polymer precipitation. In this work we investigate the molecular origin of such cooperativity and the evolution of the hydration pattern in the undercooled polymer solution. The solution behaviour of an atactic 30-mer at high dilution is studied in the temperature interval from 243 to 323 K with a favourable comparison to available experimental data. In the water soluble states of PNIPAM we detect a correlation between polymer segmental dynamics and diffusion motion of bound water, occurring with the same activation energy. Simulation results show that below the coil-to-globule transition temperature PNIPAM is surrounded by a network of hydrogen bonded water molecules and that the cooperativity arises from the structuring of water clusters in proximity to hydrophobic groups. Differently, the perturbation of the hydrogen bond pattern involving water and amide groups occurs above the transition temperature. Altogether these findings reveal that even above the LCST PNIPAM remains largely hydrated and that the coil-to-globule transition is related with a significant rearrangement of the solvent in the proximity of the surface of the polymer. The comparison between the hydrogen bonding of water in the surrounding of PNIPAM isopropyl groups and in the bulk displays a decreased structuring of solvent at the hydrophobic polymer-water interface across the transition temperature, as expected because of the topological extension along the chain of such interface. No evidence of an upper critical solution temperature behaviour, postulated in theoretical and thermodynamics studies of PNIPAM aqueous solution, is observed in the low temperature domain.

The molecular dynamics simulation on the mechanical properties of Ni glass with external pressure

NASA Astrophysics Data System (ADS)

Zhang, Chuan-Hui; Wang, Ying; Sun, Dong-Bai

2017-08-01

In this paper, rapid quenching of Ni from crystal to metallic glass (MG) at different external pressures is simulated by molecular dynamics. The pair distribution functions (PDFs), mean-square displacement, glass transition temperature (Tg) and elastic property are calculated and compared with each other. The split of the second PDF peak means the liquid’s transition to glass state starts as previously reported for other MGs. And the Ri/R1 ratio rule is found to hold very well in Ni MG and reveals the SPO structural feature in the configurations. Moreover, with high external pressure, Tg values are more approximated by density-temperature and enthalpy-temperature curves. At last, the elastic modulus and mechanics modulus of quenching models produced a monotonous effect with increasing external pressure and temperature.

Resonance dynamical intermolecular interaction in the crystals of pure and binary mixture n-paraffins

NASA Astrophysics Data System (ADS)

Puchkovska, G. O.; Danchuk, V. D.; Makarenko, S. P.; Kravchuk, A. P.; Kotelnikova, E. N.; Filatov, S. K.

2004-12-01

In the present paper, we report temperature dependent FTIR spectra studies of Davydov splitting value for CH 2 rocking vibrations of pure crystalline n-paraffins C nH 2 n+2 ( n is the number of carbon atoms) and some isomorphically substituted binary mixtures of n-paraffins C 22H 46:C 24H 50. Temperature dependencies of Davydov splitting value have been shown to be characterized by the amount of irregularities (sharp decreasing), which corresponds to the phase transitions into the high-temperature (hexagonal) state for pure n-paraffins or different rotator crystalline states for the mixtures. Statistic and dynamic models have been proposed, which provides an adequate description of the observed effect. In the framework of these models, two different mechanisms are responsible for the temperature behavior of the vibrational mode splitting value. Besides the thermal expansion of crystals at heating, the quenching of vibrational excitons on the orientational defects of different nature takes place, accompanied with the breakage of the crystal lattice translational symmetry. The creation of such defects is resulted from the excitation of librational and rotational molecular degrees of freedom at the crystal polymorphic transitions into different rotary crystalline states. The manifestation of the resonance dynamical intermolecular interaction in the spectra of intramolecular vibrations in these crystals has been theoretically analyzed in terms of stochastic equations, taking into consideration the above mentioned phase transition. We have obtained the explicit expression for the theoretically predicted dependence of Davydov splitting value on temperature. The absorption bands, corresponding to Davydov splitting components, have been shown to approach rapidly each other at the transition to the high-temperature (hexagonal) phase. Computer simulation of such dependence has been performed for some aliphatic compounds. Good agreement between the experimental and computer simulation results has been obtained. The theoretical approach developed in the present paper for the resonance dynamical intermolecular interaction near such transitions from the three-dimensional to one-dimensional phase of crystalline n-paraffins has a general character and can be applied to the description of some specific features observed in the vibrational spectra of rotary crystals.

Gravitation waves from QCD and electroweak phase transitions

NASA Astrophysics Data System (ADS)

Chen, Yidian; Huang, Mei; Yan, Qi-Shu

2018-05-01

We investigate the gravitation waves produced from QCD and electroweak phase transitions in the early universe by using a 5-dimension holographic QCD model and a holographic technicolor model. The dynamical holographic QCD model is to describe the pure gluon system, where a first order confinement-deconfinement phase transition can happen at the critical temperature around 250 MeV. The minimal holographic technicolor model is introduced to model the strong dynamics of electroweak, it can give a first order electroweak phase transition at the critical temperature around 100-360 GeV. We find that for both GW signals produced from QCD and EW phase transitions, in the peak frequency region, the dominant contribution comes from the sound waves, while away from the peak frequency region the contribution from the bubble collision is dominant. The peak frequency of gravitation wave determined by the QCD phase transition is located around 10-7 Hz which is within the detectability of FAST and SKA, and the peak frequency of gravitational wave predicted by EW phase transition is located at 0.002 - 0.007 Hz, which might be detectable by BBO, DECIGO, LISA and ELISA.

Effects of steaming treatment on crystallinity and glass transition temperature of Eucalyptuses grandis × E. urophylla

NASA Astrophysics Data System (ADS)

Kong, Lulu; Zhao, Zijian; He, Zhengbin; Yi, Songlin

To investigate the effects of steaming treatment on crystallinity and glass transition temperature, samples of Eucalyptuses grandis × E. urophylla with moisture content of 50%, 70%, and 90% were steamed in saturated steam at 100 °C for 2, 4, 6, and 8 h. The degree of crystallinity (CrI) and glass transition temperature (Tg) were measured via X-ray diffraction and dynamic mechanical analysis, respectively. Results revealed a crystallinity degree of Eucalyptus of 29.9%-34.2%, and a glass transition temperature of 80-94 °C with moisture contents of steamed samples of 20%. Furthermore, steaming was revealed to have an obvious effect on crystallization and glass transition. Values of CrI and Tg showed similar changing characteristics: increasing initially, followed by a decrease with increasing steaming time, reaching a maximum at 2 h. Water within the wood seemed to promote crystallization and glass transition during steaming. All steamed samples tested in this study reached glass transition temperature after 50 min of steaming, and the residual growth stress was released.

Impact of the glass transition on exciton dynamics in polymer thin films

NASA Astrophysics Data System (ADS)

Ehrenreich, Philipp; Proepper, Daniel; Graf, Alexander; Jores, Stefan; Boris, Alexander V.; Schmidt-Mende, Lukas

2017-11-01

In the development of organic electronics, unlimited design possibilities of conjugated polymers offer a wide variety of mechanical and electronic properties. Thereby, it is crucially important to reveal universal physical characteristics that allow efficient and forward developments of new chemical compounds. In particular for organic solar cells, a deeper understanding of exciton dynamics in polymer films can help to improve the charge generation process further. For this purpose, poly(3-hexylthiophene) (P3HT) is commonly used as a model system, although exciton decay kinetics have found different interpretations. Using temperature-dependent time-resolved photoluminescence spectroscopy in combination with low-temperature spectroscopic ellipsometry, we can show that P3HT is indeed a model system in which excitons follow a simple diffusion/hopping model. Based on our results we can exclude the relevance of hot-exciton emission as well as a dynamic torsional relaxation upon photoexcitation on a ps time scale. Instead, we depict the glass transition temperature of polymers to strongly affect exciton dynamics.

Pulsating gliding transition in the dynamics of levitating liquid nitrogen droplets

NASA Astrophysics Data System (ADS)

Snezhko, Alexey; Ben Jacob, Eshel; Aranson, Igor S.

2008-04-01

Hot surfaces can cause levitation of small liquid droplets if the temperature is kept above the Leidenfrost point (220 °C for water) due to the pressure formed because of rapid evaporation. Here, we demonstrate a new class of pulsating-gliding dynamic transitions in a special setting of the Leidenfrost effect at room temperatures and above a viscous fluid for droplets of liquid nitrogen. A whole range of highly dynamic patterns unfolds when droplets of liquid nitrogen are poured on the surface of another, more viscous liquid at room temperature. We also discovered that the levitating droplets induce vortex motion in the supporting viscous liquid. Depending on the viscosity of the supporting liquid, the nitrogen droplets either adopt an oscillating (pulsating) star-like shape with different azimuthal symmetries (from 2-9 petals) or glide on the surface with random trajectories. Thus, by varying the viscosity of the supporting liquid, we achieve controlled morphology and dynamics of Leidenfrost droplets.

Thermal characterization of static and dynamical properties of the confined molecular systems interacting through dispersion force.

PubMed

Ramos, Sergio Luis L M; Ogino, Michihiko; Oguni, Masaharu

2015-01-28

We investigated the thermal properties of liquid methylcyclohexane and racemic sec-butylcyclohexane, as representatives of a molecular system with only dispersion-force intermolecular interactions, confined in the pores (thickness/diameter d = 12, 6, 1.1 nm) of silica gels by adiabatic calorimetry. The results imply a heterogeneous picture for molecular aggregate under confinement consisting of an interfacial region and an inner pore one. In the vicinity of a glass-transition temperature T(g,bulk) of bulk liquid, two distinguishable relaxation phenomena were observed for the confined systems and their origins were attributed to the devitrification, namely glass transition, processes of (1) a layer of interfacial molecules adjacent to the pore walls and (2) the molecules located in the middle of the pore. A third glass-transition phenomenon was observed at lower temperatures and ascribed to a secondary relaxation process. The glass transition of the interfacial-layer molecules was found to proceed at temperatures rather above T(g,bulk), whereas that of the molecules located in the inner pore region occurred at temperatures below T(g,bulk). We discuss the reason why the molecules located in different places in the pores reveal the respectively different dynamical properties.

The effect of moisture on the dynamic thermomechanical properties of a graphite/epoxy composite

NASA Technical Reports Server (NTRS)

Sykes, G. F.; Burks, H. D.; Nelson, J. B.

1977-01-01

A study has been made of the effect of moisture absorption on the dynamic thermomechanical properties of a graphite/epoxy composite recently considered for building primary aircraft structures. Torsional braid analysis (TBA) and thermomechanical analysis (TMA) techniques were used to measure changes in the glass transition temperature (Tg) and the initial softening temperature (heat distortion temperature, HDT) of T-300/5209 graphite/epoxy composites exposed to room temperature water soak.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glynos, Emmanouil; Johnson, Kyle J.; Frieberg, Bradley

Here, the surface relaxation dynamics of supported star-shaped polymer thin films are shown to be slower than the bulk, persisting up to temperatures at least 50 degrees above the bulk glass transition temperature Tmore » $$bulk\\atop{g}$$. This behavior, exhibited by star-shaped polystyrenes (SPSs) with functionality f = 8 arms and molecular weights per arm M arm < M e (M e is the entanglement molecular weight), is shown by molecular dynamics simulations to be associated with a preferential localization of these macromolecules at the free surface. This new phenomenon is in notable contrast to that of linear chain polymer thin film systems where the surface relaxations are enhanced in relation to the bulk; this enhancement persists only for a limited temperature range above the bulk T$$bulk\\atop{g}$$. Finally, evidence of the slow surface dynamics, compared to the bulk, for temperatures well above T g and at length and time scales not associated with the glass transition has not previously been reported for polymers.« less

Free Surface Relaxations of Star-Shaped Polymer Films

DOE PAGES

Glynos, Emmanouil; Johnson, Kyle J.; Frieberg, Bradley; ...

2017-11-28

Here, the surface relaxation dynamics of supported star-shaped polymer thin films are shown to be slower than the bulk, persisting up to temperatures at least 50 degrees above the bulk glass transition temperature Tmore » $$bulk\\atop{g}$$. This behavior, exhibited by star-shaped polystyrenes (SPSs) with functionality f = 8 arms and molecular weights per arm M arm < M e (M e is the entanglement molecular weight), is shown by molecular dynamics simulations to be associated with a preferential localization of these macromolecules at the free surface. This new phenomenon is in notable contrast to that of linear chain polymer thin film systems where the surface relaxations are enhanced in relation to the bulk; this enhancement persists only for a limited temperature range above the bulk T$$bulk\\atop{g}$$. Finally, evidence of the slow surface dynamics, compared to the bulk, for temperatures well above T g and at length and time scales not associated with the glass transition has not previously been reported for polymers.« less

Low temperature phase of the trigonal RbIn(MoO4)2 crystal

NASA Astrophysics Data System (ADS)

Zapart, W.; Zapart, M. B.; Schranz, W.; Reinecker, M.

2013-02-01

The present article is devoted to a new low-temperature phase transition found at about T pt = 84 K in the layered RbIn(MoO4)2 crystal. This phase transition is well proved by dynamical mechanical analysis through anomalies in the temperature behaviour of both real and imaginary parts of the Young's modulus. From the polarizing microscope observations it was found that below T pt the ferroelastic phase disappears. This transition has also been seen through strong changes in the shape of the electron paramagnetic resonance lines. EPR studies, performed in the liquid nitrogen temperature, yield evidence of strong rebuilding of the crystal unit cell in comparison with that of the high temperature paraelastic phase.

Dynamical transition, hydrophobic interface, and the temperature dependence of electrostatic fluctuations in proteins.

PubMed

Lebard, David N; Matyushov, Dmitry V

2008-12-01

Molecular dynamics simulations have revealed a dramatic increase, with increasing temperature, of the amplitude of electrostatic fluctuations caused by water at the active site of metalloprotein plastocyanin. The increased breadth of electrostatic fluctuations, expressed in terms of the reorganization energy of changing the redox state of the protein, is related to the formation of the hydrophobic protein-water interface, allowing large-amplitude collective fluctuations of the water density in the protein's first solvation shell. On top of the monotonic increase of the reorganization energy with increasing temperature, we have observed a spike at approximately 220 K also accompanied by a significant slowing of the exponential collective Stokes shift dynamics. In contrast to the local density fluctuations of the hydration-shell waters, these spikes might be related to the global property of the water solvent crossing the Widom line or undergoing a weak first-order transition.

Predicting Crystallization of Amorphous Drugs with Terahertz Spectroscopy.

PubMed

Sibik, Juraj; Löbmann, Korbinian; Rades, Thomas; Zeitler, J Axel

2015-08-03

There is a controversy about the extent to which the primary and secondary dielectric relaxations influence the crystallization of amorphous organic compounds below the glass transition temperature. Recent studies also point to the importance of fast molecular dynamics on picosecond-to-nanosecond time scales with respect to the glass stability. In the present study we provide terahertz spectroscopy evidence on the crystallization of amorphous naproxen well below its glass transition temperature and confirm the direct role of Johari-Goldstein (JG) secondary relaxation as a facilitator of the crystallization. We determine the onset temperature Tβ above which the JG relaxation contributes to the fast molecular dynamics and analytically quantify the level of this contribution. We then show there is a strong correlation between the increase in the fast molecular dynamics and onset of crystallization in several chosen amorphous drugs. We believe that this technique has immediate applications to quantify the stability of amorphous drug materials.

Can xenon in water inhibit ice growth? Molecular dynamics of phase transitions in water-Xe system.

PubMed

Artyukhov, Vasilii I; Pulver, Alexander Yu; Peregudov, Alex; Artyuhov, Igor

2014-07-21

Motivated by recent experiments showing the promise of noble gases as cryoprotectants, we perform molecular dynamics modeling of phase transitions in water with xenon under cooling. We follow the structure and dynamics of xenon water solution as a function of temperature. Homogeneous nucleation of clathrate hydrate phase is observed and characterized. As the temperature is further reduced we observe hints of dissociation of clathrate due to stronger hydrophobic hydration, pointing towards a possible instability of clathrate at cryogenic temperatures and conversion to an amorphous phase comprised of "xenon + hydration shell" Xe·(H2O)21.5 clusters. Simulations of ice-xenon solution interface in equilibrium and during ice growth reveal the effects of xenon on the ice-liquid interface, where adsorbed xenon causes roughening of ice surface but does not preferentially form clathrate. These results provide evidence against the ice-blocker mechanism of xenon cryoprotection.

Organization versus frustration: low temperature transitions in a gelatine-based gel

NASA Astrophysics Data System (ADS)

Philipp, M.; Müller, U.; Sanctuary, R.; Baller, J.; Krüger, J. K.

2008-09-01

A commercial physical gel composed of gelatine, water and glycerol shows a sol-gel transition which has been resolved by optical rotation measurements by step-wise heating the gel. This transition is not observable in the longitudinal acoustic mode measured at hypersonic frequencies with Brillouin spectroscopy. Depending on the thermal treatment of the investigated material during the sol-gel transition and within the gel state, Brillouin spectroscopy reflects tremendously different hypersonic dynamics. These distinct dynamics are responsible for the formation of different glassy states at low temperatures including that of a glass-ceramic. The large variety of super-cooled and glassy states is attributed to distinct distributions of the gel's constituents within the samples. Surprisingly, the same gel state can be produced either by annealing the gel over months or by the non-equilibrium effect of thermo-diffusion (Soret effect) in the course of some minutes.

Molecular dynamics study of dual-phase microstructure of Titanium and Zirconium metals during the quenching process

NASA Astrophysics Data System (ADS)

Miyazaki, Narumasa; Sato, Kazunori; Shibutani, Yoji

Dual-phase (DP) transformation, which is composed of felite- and/or martensite- multicomponent microstructural phases, is one of the most effective tools to product functional alloys. To obtain this DP structure such as DP steels and other materials, we usually apply thermal processes such as quenching, tempering and annealing. As the transformation dynamics of DP microstructure depends on conditions of temperature, annealing time, and quenching rate, physical properties of materials are able to be tuned by controlling microstructure type, size, their interfaces and so on. In this study, to understand the behavior of DP transformation and to control physical properties of materials by tuning DP microstructures, we analyze the atomistic dynamics of DP transformation during the quenching process and the detail of DP microstructures by using the molecular dynamics simulations. As target metals of DP transformation, we focus on group 4 transition metals, such as Ti and Zr described by EAM interatomic potentials. For Ti and Zr models we perform molecular dynamics simulations by assuming melt-quenching process from 3000 K to 0 K under the isothermal-isobaric ensemble. During the process for each material, we observe liquid to HCP like transition around the melting temperature, and continuously HCP-BCC like transition around martensitic transformation temperature. Furthermore, we clearly distinguish DP microstructure for each quenched model.

Avoided criticality and slow relaxation in frustrated two-dimensional models

DOE PAGES

Esterlis, Ilya; Kivelson, Steven A.; Tarjus, Gilles

2017-10-23

Here, frustration and the associated phenomenon of “avoided criticality” have been proposed as an explanation for the dramatic relaxation slowdown in glass-forming liquids. To test this, we have undertaken a Monte Carlo study of possibly the simplest such problem, the two-dimensional XY model with frustration corresponding to a small flux f per plaquette. At f = 0, there is a Berezinskii-Kosterlitz-Thouless transition at T*, but at any small but nonzero f, this transition is avoided and replaced (presumably) by a vortex-ordering transition at much lower temperatures. We thus have studied the evolution of the dynamics for small and moderate fmore » as the system is cooled from above T* to below. Although we do find strongly temperature-dependent slowing of the dynamics as T crosses T* and that simultaneously the dynamics becomes more complex, neither effect is anywhere nearly as dramatic as the corresponding phenomena in glass-forming liquids. At the very least, this implies that the properties of supercooled liquids must depend on more than frustration and the existence of an avoided transition.« less

Simulated glass transition of poly(ethylene oxide) bulk and film: a comparative study.

PubMed

Wu, Chaofu

2011-09-29

Stepwise cooling molecular dynamics (MD) simulations have been carried out on the bulk and film models for poly(ethylene oxide) (PEO) to understand glass transition of amorphous polymer films. Three types of properties--density, energy, and dynamics--are computed and plotted against the temperature for the two systems. It has been confirmed that all these properties can reveal glass transition in both PEO bulk and film systems. All the determined glass transition temperatures (T(g)'s) drop in the same order of magnitude to the experimental data available. Among various methods, the T(g)'s obtained from the density and energy data are close to each other if the same space regions are defined, which can suggest the same free volume theory, and dynamic T(g)'s obtained from mean-squared displacements (MSDs) are highest, which can suggest the kinetic theory for structural relaxation. Consistently, all these T(g)'s obtained using different methods show that the T(g)'s of PEO film are lower than those of PEO bulk. The free surface layers of polymer films dictate this offset. © 2011 American Chemical Society

Temperature-Dependent Dielectric Properties of Al/Epoxy Nanocomposites

NASA Astrophysics Data System (ADS)

Wang, Zijun; Zhou, Wenying; Sui, Xuezhen; Dong, Lina; Cai, Huiwu; Zuo, Jing; Chen, Qingguo

2016-06-01

Broadband dielectric spectroscopy was carried out to study the transition in electrical properties of Al/epoxy nanocomposites over the frequency range of 1-107 Hz and the temperature range of -20°C to 200°C. The dielectric permittivity, dissipation factor, and electrical conductivity of the nanocomposites increased with temperature and showed an abrupt increase around the glass transition temperature ( T g). The results clearly reveal an interesting transition of the electrical properties with increasing temperature: insulator below 70°C, conductor at about 70°C. The behavior of the transition in electrical properties of the nanocomposites was explored at different temperatures. The presence of relaxation peaks in the loss tangent and electric modulus spectra of the nanocomposites confirms that the chain segmental dynamics of the polymer is accompanied by the absorption of energy given to the system. It is suggested that the temperature-dependent transition of the electric properties in the nanocomposite is closely associated with the α-relaxation. The large increase in the dissipation factor and electric conductivity depends on the direct current conduction of thermally activated charge carriers resulting from the epoxy matrix above T g.

Anomalous glassy dynamics in simple models of dense biological tissue

NASA Astrophysics Data System (ADS)

Sussman, Daniel M.; Paoluzzi, M.; Marchetti, M. Cristina; Manning, M. Lisa

2018-02-01

In order to understand the mechanisms for glassy dynamics in biological tissues and shed light on those in non-biological materials, we study the low-temperature disordered phase of 2D vertex-like models. Recently it has been noted that vertex models have quite unusual behavior in the zero-temperature limit, with rigidity transitions that are controlled by residual stresses and therefore exhibit very different scaling and phenomenology compared to particulate systems. Here we investigate the finite-temperature phase of two-dimensional Voronoi and Vertex models, and show that they have highly unusual, sub-Arrhenius scaling of dynamics with temperature. We connect the anomalous glassy dynamics to features of the potential energy landscape associated with zero-temperature inherent states.

Effects of adding LiBF4 on the glass-transition kinetics of 1,2-propanediol

NASA Astrophysics Data System (ADS)

Terashima, Yukio; Takeda, Kiyoshi

2017-11-01

By applying an isoconversional method to differential-scanning calorimetry (DSC) data, we have discovered that the addition of LiBF4 significantly affects the activation energy Eα of the glass transition of 1,2-propanediol. Depending upon its concentration, the dynamics of the glass transition are affected more by adding LiBF4 at an early stage of the glass-to-liquid transition rather than at later stages. As the mole fraction x of LiBF4 increases, the value of Eα initially increases, but it decreases dramatically during the glass transition. The abrupt decline in Eα suggests that the addition of LiBF4 breaks cooperative rearranging motions into smaller parts. The expansion of cooperativity, and its fragmentation with increasing temperature, can be explained in terms of competition between the hydrogen-bond networks of the alcohol solvent and the ionic interactions due to the added salt. The variability of Eα with temperature is found to correlate exponentially with the dynamic fragility.

Estimating Arrhenius parameters using temperature programmed molecular dynamics.

PubMed

Imandi, Venkataramana; Chatterjee, Abhijit

2016-07-21

Kinetic rates at different temperatures and the associated Arrhenius parameters, whenever Arrhenius law is obeyed, are efficiently estimated by applying maximum likelihood analysis to waiting times collected using the temperature programmed molecular dynamics method. When transitions involving many activated pathways are available in the dataset, their rates may be calculated using the same collection of waiting times. Arrhenius behaviour is ascertained by comparing rates at the sampled temperatures with ones from the Arrhenius expression. Three prototype systems with corrugated energy landscapes, namely, solvated alanine dipeptide, diffusion at the metal-solvent interphase, and lithium diffusion in silicon, are studied to highlight various aspects of the method. The method becomes particularly appealing when the Arrhenius parameters can be used to find rates at low temperatures where transitions are rare. Systematic coarse-graining of states can further extend the time scales accessible to the method. Good estimates for the rate parameters are obtained with 500-1000 waiting times.

Quantum Quench Dynamics in the Transverse Field Ising Model at Non-zero Temperatures

NASA Astrophysics Data System (ADS)

Abeling, Nils; Kehrein, Stefan

The recently discovered Dynamical Phase Transition denotes non-analytic behavior in the real time evolution of quantum systems in the thermodynamic limit and has been shown to occur in different systems at zero temperature [Heyl et al., Phys. Rev. Lett. 110, 135704 (2013)]. In this talk we present the extension of the analysis to non-zero temperature by studying a generalized form of the Loschmidt echo, the work distribution function, of a quantum quench in the transverse field Ising model. Although the quantitative behavior at non-zero temperatures still displays features derived from the zero temperature non-analyticities, it is shown that in this model dynamical phase transitions do not exist if T > 0 . This is a consequence of the system being initialized in a thermal state. Moreover, we elucidate how the Tasaki-Crooks-Jarzynski relation can be exploited as a symmetry relation for a global quench or to obtain the change of the equilibrium free energy density. This work was supported through CRC SFB 1073 (Project B03) of the Deutsche Forschungsgemeinschaft (DFG).

LaAlO3: A substrate material with unusual ferroelastic properties

NASA Astrophysics Data System (ADS)

Kustov, S.; Liubimova, Iu.; Salje, E. K. H.

2018-01-01

Twin boundary dynamics in LaAlO3 is associated with non-linear anelasticity. Ultrasonic studies of non-linear twin boundary dynamics between 80 and 520 K show that cooling substrates from temperatures near the ferroelastic transition at 813 K generate three characteristic thermal regimes with different non-linear dynamics. Twin boundaries are initially highly mobile. Anelastic strain amplitudes versus stress are power law distributed with an exponent of 2.5. No de-pinning was found down to elastic strain amplitudes of ɛ0 ˜ 10-7. The power law is gradually replaced between 370 K and 280 K by few large singularities (jerks) due to massive rearrangements of the domain structure for ɛ0 larger than ca. 5 × 10-5. At lower temperatures, the domain structure is pinned with well-defined thresholds for de-pinning. The de-pinning is not accompanied by global rearrangements of twin patterns below room temperature. Unexpectedly, the low-temperature critical de-pinning strain amplitude decreases with decreasing temperature, which may indicate an additional, so far unknown phase transition near 40 K.

Relationship between local structure and relaxation in out-of-equilibrium glassy systems

DOE PAGES

Schoenholz, Samuel S.; Cubuk, Ekin D.; Kaxiras, Efthimios; ...

2016-12-27

The dynamical glass transition is typically taken to be the temperature at which a glassy liquid is no longer able to equilibrate on experimental timescales. Consequently, the physical properties of these systems just above or below the dynamical glass transition, such as viscosity, can change by many orders of magnitude over long periods of time following external perturbation. During this progress toward equilibrium, glassy systems exhibit a history dependence that has complicated their study. In previous work, we bridged the gap between structure and dynamics in glassy liquids above their dynamical glass transition temperatures by introducing a scalar field calledmore » “softness,” a quantity obtained using machine-learning methods. Softness is designed to capture the hidden patterns in relative particle positions that correlate strongly with dynamical rearrangements of particle positions. Here we show that the out-of-equilibrium behavior of a model glass-forming system can be understood in terms of softness. We first demonstrate that the evolution of behavior following a temperature quench is a primarily structural phenomenon: The structure changes considerably, but the relationship between structure and dynamics remains invariant. We then show that the relaxation time can be robustly computed from structure as quantified by softness, with the same relation holding both in equilibrium and as the system ages. Together, these results show that the history dependence of the relaxation time in glasses requires knowledge only of the softness in addition to the usual state variables.« less

Relationship between local structure and relaxation in out-of-equilibrium glassy systems.

PubMed

Schoenholz, Samuel S; Cubuk, Ekin D; Kaxiras, Efthimios; Liu, Andrea J

2017-01-10

The dynamical glass transition is typically taken to be the temperature at which a glassy liquid is no longer able to equilibrate on experimental timescales. Consequently, the physical properties of these systems just above or below the dynamical glass transition, such as viscosity, can change by many orders of magnitude over long periods of time following external perturbation. During this progress toward equilibrium, glassy systems exhibit a history dependence that has complicated their study. In previous work, we bridged the gap between structure and dynamics in glassy liquids above their dynamical glass transition temperatures by introducing a scalar field called "softness," a quantity obtained using machine-learning methods. Softness is designed to capture the hidden patterns in relative particle positions that correlate strongly with dynamical rearrangements of particle positions. Here we show that the out-of-equilibrium behavior of a model glass-forming system can be understood in terms of softness. To do this we first demonstrate that the evolution of behavior following a temperature quench is a primarily structural phenomenon: The structure changes considerably, but the relationship between structure and dynamics remains invariant. We then show that the relaxation time can be robustly computed from structure as quantified by softness, with the same relation holding both in equilibrium and as the system ages. Together, these results show that the history dependence of the relaxation time in glasses requires knowledge only of the softness in addition to the usual state variables.

Glass transition in ferroic glass K x (ND4)1-x D2PO4: a complete x-ray diffraction line shape analysis

NASA Astrophysics Data System (ADS)

Ranjan Choudhury, Rajul; Chitra, R.; Jayakrishnan, V. B.

2016-03-01

Quenching of dynamic disorder in glassy systems is termed as the glass transition. Ferroic glasses belong to the class of paracrystalline materials having crystallographic order in-between that of a perfect crystal and amorphous material, a classic example of ferroic glass is the solid solution of ferroelectric deuterated potassium dihydrogen phosphate and antiferroelectric deuterated ammonium dihydrogen phosphate. Lowering temperature of this ferroic glass can lead to a glass transition to a quenched disordered state. The subtle atomic rearrangement that takes place at such a glass transition can be revealed by careful examination of the temperature induced changes occurring in the x-ray powder diffraction (XRD) patterns of these materials. Hence we report here results of a complete diffraction line shape analysis of the XRD patterns recorded at different temperatures from deuterated mixed crystals DK x A1-x DP with mixing concentration x ranging as 0 < x < 1. Changes observed in diffraction peak shapes have been explained on the basis of structural rearrangements induced by changing O-D-O hydrogen bond dynamics in these paracrystals.

Tunable Bragg filters with a phase transition material defect layer

DOE PAGES

Wang, Xi; Gong, Zilun; Dong, Kaichen; ...

2016-01-01

We propose an all-solid-state tunable Bragg filter with a phase transition material as the defect layer. Bragg filters based on a vanadium dioxide defect layer sandwiched between silicon dioxide/titanium dioxide Bragg gratings are experimentally demonstrated. Temperature dependent reflection spectroscopy shows the dynamic tunability and hysteresis properties of the Bragg filter. Temperature dependent Raman spectroscopy reveals the connection between the tunability and the phase transition of the vanadium dioxide defect layer. This work paves a new avenue in tunable Bragg filter designs and promises more applications by combining phase transition materials and optical cavities.

Tunable Bragg filters with a phase transition material defect layer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xi; Gong, Zilun; Dong, Kaichen

We propose an all-solid-state tunable Bragg filter with a phase transition material as the defect layer. Bragg filters based on a vanadium dioxide defect layer sandwiched between silicon dioxide/titanium dioxide Bragg gratings are experimentally demonstrated. Temperature dependent reflection spectroscopy shows the dynamic tunability and hysteresis properties of the Bragg filter. Temperature dependent Raman spectroscopy reveals the connection between the tunability and the phase transition of the vanadium dioxide defect layer. This work paves a new avenue in tunable Bragg filter designs and promises more applications by combining phase transition materials and optical cavities.

Revealing the Link between Structural Relaxation and Dynamic Heterogeneity in Glass-Forming Liquids

NASA Astrophysics Data System (ADS)

Wang, Lijin; Xu, Ning; Wang, W. H.; Guan, Pengfei

2018-03-01

Despite the use of glasses for thousands of years, the nature of the glass transition is still mysterious. On approaching the glass transition, the growth of dynamic heterogeneity has long been thought to play a key role in explaining the abrupt slowdown of structural relaxation. However, it still remains elusive whether there is an underlying link between structural relaxation and dynamic heterogeneity. Here, we unravel the link by introducing a characteristic time scale hiding behind an identical dynamic heterogeneity for various model glass-forming liquids. We find that the time scale corresponds to the kinetic fragility of liquids. Moreover, it leads to scaling collapse of both the structural relaxation time and dynamic heterogeneity for all liquids studied, together with a characteristic temperature associated with the same dynamic heterogeneity. Our findings imply that studying the glass transition from the viewpoint of dynamic heterogeneity is more informative than expected.

Fundamental considerations in the effect of molecular weight on the glass transition of the gelatin/cosolute system.

PubMed

Jiang, Bin; Kasapis, Stefan; Kontogiorgos, Vassilis

2012-05-01

Four molecular fractions of gelatin produced by alkaline hydrolysis of collagen were investigated in the presence of cosolute to record the mechanical properties of the glass transition in high-solid preparations. Dynamic oscillatory and stress relaxation moduli in shear were recorded from 40°C to temperatures as low as -60°C. The small-deformation behavior of these linear polymers was separated by the method of reduced variables into a basic function of time alone and a basic function of temperature alone. The former allowed the reduction of isothermal runs into a master curve covering 17 orders of magnitude in the time domain. The latter follows the passage from the rubbery plateau through the glass transition region to the glassy state seen in the variation of shift factor, a(T) , as a function of temperature. The mechanical glass transition temperature (T(g) ) is pinpointed at the operational threshold of the free volume theory and the predictions of the reaction rate theory. Additional insights into molecular dynamics are obtained via the coupling model of cooperativity, which introduces the concept of coupling constant or interaction strength of local segmental motions that govern structural relaxation at the vicinity of T(g) . The molecular weight of the four gelatin fractions appears to have a profound effect on the transition temperature or coupling constant of vitrified matrices, as does the protein chemistry in relation to that of amorphous synthetic polymers or gelling polysaccharides. © 2011 Wiley Periodicals, Inc.

Folding thermodynamics of model four-strand antiparallel beta-sheet proteins.

PubMed Central

Jang, Hyunbum; Hall, Carol K; Zhou, Yaoqi

2002-01-01

The thermodynamic properties for three different types of off-lattice four-strand antiparallel beta-strand protein models interacting via a hybrid Go-type potential have been investigated. Discontinuous molecular dynamic simulations have been performed for different sizes of the bias gap g, an artificial measure of a model protein's preference for its native state. The thermodynamic transition temperatures are obtained by calculating the squared radius of gyration R(g)(2), the root-mean-squared pair separation fluctuation Delta(B), the specific heat C(v), the internal energy of the system E, and the Lindemann disorder parameter Delta(L). Despite these models' simplicity, they exhibit a complex set of protein transitions, consistent with those observed in experimental studies on real proteins. Starting from high temperature, these transitions include a collapse transition, a disordered-to-ordered globule transition, a folding transition, and a liquid-to-solid transition. The high temperature transitions, i.e., the collapse transition and the disordered-to-ordered globule transition, exist for all three beta-strand proteins, although the native-state geometry of the three model proteins is different. However the low temperature transitions, i.e., the folding transition and the liquid-to-solid transition, strongly depend on the native-state geometry of the model proteins and the size of the bias gap. PMID:11806908

Anomalous metastability in a temperature-driven transition

NASA Astrophysics Data System (ADS)

Ibáñez Berganza, M.; Coletti, P.; Petri, A.

2014-06-01

The Langer theory of metastability provides a description of the lifetime and properties of the metastable phase of the Ising model field-driven transition, describing the magnetic-field-driven transition in ferromagnets and the chemical-potential-driven transition of fluids. An immediate further step is to apply it to the study of a transition driven by the temperature, as the one exhibited by the two-dimensional Potts model. For this model, a study based on the analytical continuation of the free energy (Meunier J. L. and Morel A., Eur. Phys. J. B, 13 (2000) 341) predicts the anomalous vanishing of the metastable temperature range in the large-system-size limit, an issue that has been controversial since the eighties. By a GPU algorithm we compare the Monte Carlo dynamics with the theory. For temperatures close to the transition we obtain agreement and characterize the dependence on the system size, which is essentially different with respect to the Ising case. For smaller temperatures, we observe the onset of stationary states with non-Boltzmann statistics, not predicted by the theory.

Dynamic phase transitions of the Blume-Emery-Griffiths model under an oscillating external magnetic field by the path probability method

NASA Astrophysics Data System (ADS)

Ertaş, Mehmet; Keskin, Mustafa

2015-03-01

By using the path probability method (PPM) with point distribution, we study the dynamic phase transitions (DPTs) in the Blume-Emery-Griffiths (BEG) model under an oscillating external magnetic field. The phases in the model are obtained by solving the dynamic equations for the average order parameters and a disordered phase, ordered phase and four mixed phases are found. We also investigate the thermal behavior of the dynamic order parameters to analyze the nature dynamic transitions as well as to obtain the DPT temperatures. The dynamic phase diagrams are presented in three different planes in which exhibit the dynamic tricritical point, double critical end point, critical end point, quadrupole point, triple point as well as the reentrant behavior, strongly depending on the values of the system parameters. We compare and discuss the dynamic phase diagrams with dynamic phase diagrams that were obtained within the Glauber-type stochastic dynamics based on the mean-field theory.

Effects of counterion size and backbone rigidity on the dynamics of ionic polymer melts and glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Yao; Bocharova, Vera; Ma, Mengze

Backbone rigidity, counterion size and the static dielectric constant affect the glass transition temperature, segmental relaxation time and decoupling between counterion and segmental dynamics in significant manners.

Chiral phase transition from string theory.

PubMed

Parnachev, Andrei; Sahakyan, David A

2006-09-15

The low energy dynamics of a certain D-brane configuration in string theory is described at weak t'Hooft coupling by a nonlocal version of the Nambu-Jona-Lasinio model. We study this system at finite temperature and strong t'Hooft coupling, using the string theory dual. We show that for sufficiently low temperatures chiral symmetry is broken, while for temperatures larger then the critical value, it gets restored. We compute the latent heat and observe that the phase transition is of the first order.

Modeling dynamic beta-gamma polymorphic transition in Tin

NASA Astrophysics Data System (ADS)

Chauvin, Camille; Montheillet, Frank; Petit, Jacques; CEA Gramat Collaboration; EMSE Collaboration

2015-06-01

Solid-solid phase transitions in metals have been studied by shock waves techniques for many decades. Recent experiments have investigated the transition during isentropic compression experiments and shock-wave compression and have highlighted the strong influence of the loading rate on the transition. Complementary data obtained with velocity and temperature measurements around the polymorphic transition beta-gamma of Tin on gas gun experiments have displayed the importance of the kinetics of the transition. But, even though this phenomenon is known, modeling the kinetic remains complex and based on empirical formulations. A multiphase EOS is available in our 1D Lagrangian code Unidim. We propose to present the influence of various kinetic laws (either empirical or involving nucleation and growth mechanisms) and their parameters (Gibbs free energy, temperature, pressure) on the transformation rate. We compare experimental and calculated velocities and temperature profiles and we underline the effects of the empirical parameters of these models.

Thermally Driven Electronic Topological Transition in FeTi

NASA Astrophysics Data System (ADS)

Yang, F. C.; Muñoz, J. A.; Hellman, O.; Mauger, L.; Lucas, M. S.; Tracy, S. J.; Stone, M. B.; Abernathy, D. L.; Xiao, Yuming; Fultz, B.

2016-08-01

Ab initio molecular dynamics, supported by inelastic neutron scattering and nuclear resonant inelastic x-ray scattering, showed an anomalous thermal softening of the M5- phonon mode in B 2 -ordered FeTi that could not be explained by phonon-phonon interactions or electron-phonon interactions calculated at low temperatures. A computational investigation showed that the Fermi surface undergoes a novel thermally driven electronic topological transition, in which new features of the Fermi surface arise at elevated temperatures. The thermally induced electronic topological transition causes an increased electronic screening for the atom displacements in the M5- phonon mode and an adiabatic electron-phonon interaction with an unusual temperature dependence.

A molecular dynamics examination of the relationship between self-diffusion and viscosity in liquid metals.

PubMed

Lü, Yongjun; Cheng, Hao; Chen, Min

2012-06-07

The self-diffusion coefficients D and the viscosities η of elemental Ni, Cu, and Ni-Si alloys have been calculated over a wide temperature range by molecular dynamics simulations. For elemental Ni and Cu, Arrhenius-law variations of D and η with temperature dominate. The temperature dependence of Dη can be approximated by a linear relation, whereas the Stokes-Einstein relation is violated. The calculations of D and η are extended to the regions close to the crystallization of Ni(95)Si(5), Ni(90)Si(10), and the glass transitions of Ni(80)Si(20) and Ni(75)Si(25). The results show that both D and η strongly deviate from the Arrhenius law in the vicinity of phase transitions, exhibiting a power-law divergence. We find a decoupling of diffusion and viscous flow just above the crystallization of Ni(95)Si(5) and Ni(90)Si(10). For the two glass-forming alloys, Ni(80)Si(20) and Ni(75)Si(25), the relation Dη = const is obeyed as the glass transition is approached, indicating a dynamic coupling as predicted by the mode-coupling theory. This coupling is enhanced with increasing Si composition and at 25%, Si spans a wide temperature range through the melting point. The decoupling is found to be related to the distribution of local ordered structure in the melts. The power-law governing the growth of solid-like clusters prior to crystallization creates a dynamic heterogeneity responsible for decoupling.

A molecular dynamics examination of the relationship between self-diffusion and viscosity in liquid metals

NASA Astrophysics Data System (ADS)

Lü, Yongjun; Cheng, Hao; Chen, Min

2012-06-01

The self-diffusion coefficients D and the viscosities η of elemental Ni, Cu, and Ni-Si alloys have been calculated over a wide temperature range by molecular dynamics simulations. For elemental Ni and Cu, Arrhenius-law variations of D and η with temperature dominate. The temperature dependence of Dη can be approximated by a linear relation, whereas the Stokes-Einstein relation is violated. The calculations of D and η are extended to the regions close to the crystallization of Ni95Si5, Ni90Si10, and the glass transitions of Ni80Si20 and Ni75Si25. The results show that both D and η strongly deviate from the Arrhenius law in the vicinity of phase transitions, exhibiting a power-law divergence. We find a decoupling of diffusion and viscous flow just above the crystallization of Ni95Si5 and Ni90Si10. For the two glass-forming alloys, Ni80Si20 and Ni75Si25, the relation Dη = const is obeyed as the glass transition is approached, indicating a dynamic coupling as predicted by the mode-coupling theory. This coupling is enhanced with increasing Si composition and at 25%, Si spans a wide temperature range through the melting point. The decoupling is found to be related to the distribution of local ordered structure in the melts. The power-law governing the growth of solid-like clusters prior to crystallization creates a dynamic heterogeneity responsible for decoupling.

EFFECTS OF TRITIUM GAS EXPOSURE ON THE GLASS TRANSITION TEMPERATURE OF EPDM ELASTOMER AND ON THE CONDUCTIVITY OF POLYANILINE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clark, E; Marie Kane, M

2008-12-12

Four formulations of EPDM (ethylene-propylene diene monomer) elastomer were exposed to tritium gas initially at one atmosphere and ambient temperature for between three and four months in closed containers. Material properties that were characterized include density, volume, mass, appearance, flexibility, and dynamic mechanical properties. The glass transition temperature was determined by analysis of the dynamic mechanical property data per ASTM standards. EPDM samples released significant amounts of gas when exposed to tritium, and the glass transition temperature increased by about 3 C. during the exposure. Effects of ultraviolet and gamma irradiation on the surface electrical conductivity of two types ofmore » polyaniline films are also documented as complementary results to planned tritium exposures. Future work will determine the effects of tritium gas exposure on the electrical conductivity of polyaniline films, to demonstrate whether such films can be used as a sensor to detect tritium. Surface conductivity was significantly reduced by irradiation with both gamma rays and ultraviolet light. The results of the gamma and UV experiments will be correlated with the tritium exposure results.« less

Temperature dependence of the Urbach optical absorption edge: A theory of multiple phonon absorption and emission sidebands

NASA Astrophysics Data System (ADS)

Grein, C. H.; John, Sajeev

1989-01-01

The optical absorption coefficient for subgap electronic transitions in crystalline and disordered semiconductors is calculated by first-principles means with use of a variational principle based on the Feynman path-integral representation of the transition amplitude. This incorporates the synergetic interplay of static disorder and the nonadiabatic quantum dynamics of the coupled electron-phonon system. Over photon-energy ranges of experimental interest, this method predicts accurate linear exponential Urbach behavior of the absorption coefficient. At finite temperatures the nonlinear electron-phonon interaction gives rise to multiple phonon emission and absorption sidebands which accompany the optically induced electronic transition. These sidebands dominate the absorption in the Urbach regime and account for the temperature dependence of the Urbach slope and energy gap. The physical picture which emerges is that the phonons absorbed from the heat bath are then reemitted into a dynamical polaronlike potential well which localizes the electron. At zero temperature we recover the usual polaron theory. At high temperatures the calculated tail is qualitatively similar to that of a static Gaussian random potential. This leads to a linear relationship between the Urbach slope and the downshift of the extrapolated continuum band edge as well as a temperature-independent Urbach focus. At very low temperatures, deviations from these rules are predicted arising from the true quantum dynamics of the lattice. Excellent agreement is found with experimental data on c-Si, a-Si:H, a-As2Se3, and a-As2S3. Results are compared with a simple physical argument based on the most-probable-potential-well method.

Determination of the glass-transition temperature of proteins from a viscometric approach.

PubMed

Monkos, Karol

2015-03-01

All fully hydrated proteins undergo a distinct change in their dynamical properties at glass-transition temperature Tg. To determine indirectly this temperature for dry albumins, the viscosity measurements of aqueous solutions of human, equine, ovine, porcine and rabbit serum albumin have been conducted at a wide range of concentrations and at temperatures ranging from 278 K to 318 K. Viscosity-temperature dependence of the solutions is discussed on the basis of the three parameters equation resulting from Avramov's model. One of the parameter in the Avramov's equation is the glass-transition temperature. For all studied albumins, Tg of a solution monotonically increases with increasing concentration. The glass-transition temperature of a solution depends both on Tg for a dissolved dry protein Tg,p and water Tg,w. To obtain Tg,p for each studied albumin the modified Gordon-Taylor equation was applied. This equation describes the dependence of Tg of a solution on concentration, and Tg,p and a parameter depending on the strength of the protein-solvent interaction are the fitting parameters. Thus determined the glass-transition temperature for the studied dry albumins is in the range (215.4-245.5)K. Copyright © 2014 Elsevier B.V. All rights reserved.

Experimental evidence for stochastic switching of supercooled phases in NdNiO3 nanostructures

NASA Astrophysics Data System (ADS)

Kumar, Devendra; Rajeev, K. P.; Alonso, J. A.

2018-03-01

A first-order phase transition is a dynamic phenomenon. In a multi-domain system, the presence of multiple domains of coexisting phases averages out the dynamical effects, making it nearly impossible to predict the exact nature of phase transition dynamics. Here, we report the metal-insulator transition in samples of sub-micrometer size NdNiO3 where the effect of averaging is minimized by restricting the number of domains under study. We observe the presence of supercooled metallic phases with supercooling of 40 K or more. The transformation from the supercooled metallic to the insulating state is a stochastic process that happens at different temperatures and times in different experimental runs. The experimental results are understood without incorporating material specific properties, suggesting that the behavior is of universal nature. The size of the sample needed to observe individual switching of supercooled domains, the degree of supercooling, and the time-temperature window of switching are expected to depend on the parameters such as quenched disorder, strain, and magnetic field.

Molecular Motor-Induced Instabilities and Cross Linkers Determine Biopolymer Organization

PubMed Central

Smith, D.; Ziebert, F.; Humphrey, D.; Duggan, C.; Steinbeck, M.; Zimmermann, W.; Käs, J.

2007-01-01

All eukaryotic cells rely on the active self-organization of protein filaments to form a responsive intracellular cytoskeleton. The necessity of motility and reaction to stimuli additionally requires pathways that quickly and reversibly change cytoskeletal organization. While thermally driven order-disorder transitions are, from the viewpoint of physics, the most obvious method for controlling states of organization, the timescales necessary for effective cellular dynamics would require temperatures exceeding the physiologically viable temperature range. We report a mechanism whereby the molecular motor myosin II can cause near-instantaneous order-disorder transitions in reconstituted cytoskeletal actin solutions. When motor-induced filament sliding diminishes, the actin network structure rapidly and reversibly self-organizes into various assemblies. Addition of stable cross linkers was found to alter the architectures of ordered assemblies. These isothermal transitions between dynamic disorder and self-assembled ordered states illustrate that the interplay between passive crosslinking and molecular motor activity plays a substantial role in dynamic cellular organization. PMID:17604319

Body and brain temperature coupling: the critical role of cerebral blood flow

PubMed Central

Ackerman, Joseph J. H.; Yablonskiy, Dmitriy A.

2010-01-01

Direct measurements of deep-brain and body-core temperature were performed on rats to determine the influence of cerebral blood flow (CBF) on brain temperature regulation under static and dynamic conditions. Static changes of CBF were achieved using different anesthetics (chloral hydrate, CH; α-chloralose, αCS; and isoflurane, IF) with αCS causing larger decreases in CBF than CH and IF; dynamic changes were achieved by inducing transient hypercapnia (5% CO2 in 40% O2 and 55% N2). Initial deep-brain/body-core temperature differentials were anesthetic-type dependent with the largest differential observed with rats under αCS anesthesia (ca. 2°C). Hypercapnia induction raised rat brain temperature under all three anesthesia regimes, but by different anesthetic-dependent amounts correlated with the initial differentials—αCS anesthesia resulted in the largest brain temperature increase (0.32 ± 0.08°C), while CH and IF anesthesia lead to smaller increases (0.12 ± 0.03 and 0.16 ± 0.05°C, respectively). The characteristic temperature transition time for the hypercapnia-induced temperature increase was 2–3 min under CH and IF anesthesia and ~4 min under αCS anesthesia. We conclude that both, the deep-brain/body-core temperature differential and the characteristic temperature transition time correlate with CBF: a lower CBF promotes higher deep-brain/body-core temperature differentials and, upon hypercapnia challenge, longer characteristic transition times to increased temperatures. PMID:19277681

Body and brain temperature coupling: the critical role of cerebral blood flow.

PubMed

Zhu, Mingming; Ackerman, Joseph J H; Yablonskiy, Dmitriy A

2009-08-01

Direct measurements of deep-brain and body-core temperature were performed on rats to determine the influence of cerebral blood flow (CBF) on brain temperature regulation under static and dynamic conditions. Static changes of CBF were achieved using different anesthetics (chloral hydrate, CH; alpha-chloralose, alphaCS; and isoflurane, IF) with alphaCS causing larger decreases in CBF than CH and IF; dynamic changes were achieved by inducing transient hypercapnia (5% CO(2) in 40% O(2) and 55% N(2)). Initial deep-brain/body-core temperature differentials were anesthetic-type dependent with the largest differential observed with rats under alphaCS anesthesia (ca. 2 degrees C). Hypercapnia induction raised rat brain temperature under all three anesthesia regimes, but by different anesthetic-dependent amounts correlated with the initial differentials--alphaCS anesthesia resulted in the largest brain temperature increase (0.32 +/- 0.08 degrees C), while CH and IF anesthesia lead to smaller increases (0.12 +/- 0.03 and 0.16 +/- 0.05 degrees C, respectively). The characteristic temperature transition time for the hypercapnia-induced temperature increase was 2-3 min under CH and IF anesthesia and approximately 4 min under alphaCS anesthesia. We conclude that both, the deep-brain/body-core temperature differential and the characteristic temperature transition time correlate with CBF: a lower CBF promotes higher deep-brain/body-core temperature differentials and, upon hypercapnia challenge, longer characteristic transition times to increased temperatures.

Filling-driven Mott transition in SU(N ) Hubbard models

NASA Astrophysics Data System (ADS)

Lee, Seung-Sup B.; von Delft, Jan; Weichselbaum, Andreas

2018-04-01

We study the filling-driven Mott transition involving the metallic and paramagnetic insulating phases in SU (N ) Fermi-Hubbard models, using the dynamical mean-field theory and the numerical renormalization group as its impurity solver. The compressibility shows a striking temperature dependence: near the critical end-point temperature, it is strongly enhanced in the metallic phase close to the insulating phase. We demonstrate that this compressibility enhancement is associated with the thermal suppression of the quasiparticle peak in the local spectral functions. We also explain that the asymmetric shape of the quasiparticle peak originates from the asymmetry in the dynamics of the generalized doublons and holons.

Effects of the bond polarity on the structural and dynamical properties of silica-like liquids

NASA Astrophysics Data System (ADS)

Pafong Sanjon, E.; Drossel, B.; Vogel, M.

2018-03-01

Silica is a network-forming liquid that shares many properties with water due to its tetrahedral structure. It undergoes a transition from a fragile to a strong liquid as the temperature is decreased, which is accompanied by a structural change to lower density and higher tetrahedral order. In order to disentangle the effects of Coulomb and van der Waals interactions on the structure and dynamics of liquid silica, we modify the bond polarity by changing the partial charges assigned to each atom. Using molecular dynamics simulations, we show that density, tetrahedral order, and structural relaxation times decrease when reducing bond polarity. Moreover, we find that the density maximum and the fragile-to-strong transition move to lower temperatures until they eventually vanish when the partial charges are decreased below approximately 75% of their regular value. Irrespective of whether strong or fragile behavior exists, structural relaxation is governed by hopping motion at sufficiently low temperatures. As long as there is a strong regime, the energy barrier associated with strong dynamics decreases with decreasing partial charges, but the dependence on the bond polarity differs from that of the activation energy in the Arrhenius regime at high temperatures. We show that the fragile-to-strong transition is associated with structural changes occurring between the first and second coordination shells that lead to a decrease in density and an increase in tetrahedral order. In particular, independent of the value of the partial charges, the distribution of the local structures is the same at this dynamic crossover, but we find no evidence that the effect occurs upon crossing the Widom line. In the fragile regime at intermediate temperatures, the relaxation times are well described by a previously proposed model which decomposes the apparent activation energy into a constant single-particle contribution and a temperature-dependent collective contribution. However, our results for silica-like melts do not obey several common relations of the model parameters reported for molecular glass formers.

Local variation of fragility and glass transition temperature of ultra-thin supported polymer films.

PubMed

Hanakata, Paul Z; Douglas, Jack F; Starr, Francis W

2012-12-28

Despite extensive efforts, a definitive picture of the glass transition of ultra-thin polymer films has yet to emerge. The effect of film thickness h on the glass transition temperature T(g) has been widely examined, but this characterization does not account for the fragility of glass-formation, which quantifies how rapidly relaxation times vary with temperature T. Accordingly, we simulate supported polymer films of a bead-spring model and determine both T(g) and fragility, both as a function of h and film depth. We contrast changes in the relaxation dynamics with density ρ and demonstrate the limitations of the commonly invoked free-volume layer model. As opposed to bulk polymer materials, we find that the fragility and T(g) do not generally vary proportionately. Consequently, the determination of the fragility profile--both locally and for the film as a whole--is essential for the characterization of changes in film dynamics with confinement.

Mott-to-Goodenough insulator-insulator transition in LiVO2

NASA Astrophysics Data System (ADS)

Subedi, Alaska

2017-06-01

I critically examine Goodenough's explanation for the experimentally observed phase transition in LiVO2 using microscopic calculations based on density functional and dynamical mean field theories. The high-temperature rhombohedral phase exhibits both magnetic and dynamical instabilities. Allowing a magnetic solution for the rhombohedral structure does not open an insulating gap, and an explicit treatment of the on-site Coulomb U interaction is needed to stabilize an insulating rhombohedral phase. The non-spin-polarized phonon dispersions of the rhombohedral phase show two unstable phonon modes at the wave vector (1/3 ,-1/3 ,0 ) that corresponds to the experimentally observed trimer forming instability. A full relaxation of the supercell corresponding to this instability yields a nonmagnetic state containing V3 trimers. These results are consistent with Goodenough's suggestion that the high-temperature phase is in the localized-electron regime and the transition to the low-temperature phase in the itinerant-electron regime is driven by V-V covalency.

Self-optimized construction of transition rate matrices from accelerated atomistic simulations with Bayesian uncertainty quantification

NASA Astrophysics Data System (ADS)

Swinburne, Thomas D.; Perez, Danny

2018-05-01

A massively parallel method to build large transition rate matrices from temperature-accelerated molecular dynamics trajectories is presented. Bayesian Markov model analysis is used to estimate the expected residence time in the known state space, providing crucial uncertainty quantification for higher-scale simulation schemes such as kinetic Monte Carlo or cluster dynamics. The estimators are additionally used to optimize where exploration is performed and the degree of temperature acceleration on the fly, giving an autonomous, optimal procedure to explore the state space of complex systems. The method is tested against exactly solvable models and used to explore the dynamics of C15 interstitial defects in iron. Our uncertainty quantification scheme allows for accurate modeling of the evolution of these defects over timescales of several seconds.

Aging dynamics of quantum spin glasses of rotors

NASA Astrophysics Data System (ADS)

Kennett, Malcolm P.; Chamon, Claudio; Ye, Jinwu

2001-12-01

We study the long time dynamics of quantum spin glasses of rotors using the nonequilibrium Schwinger-Keldysh formalism. These models are known to have a quantum phase transition from a paramagnetic to a spin-glass phase, which we approach by looking at the divergence of the spin-relaxation rate at the transition point. In the aging regime, we determine the dynamical equations governing the time evolution of the spin response and correlation functions, and show that all terms in the equations that arise solely from quantum effects are irrelevant at long times under time reparametrization group (RPG) transformations. At long times, quantum effects enter only through the renormalization of the parameters in the dynamical equations for the classical counterpart of the rotor model. Consequently, quantum effects only modify the out-of-equilibrium fluctuation-dissipation relation (OEFDR), i.e. the ratio X between the temperature and the effective temperature, but not the form of the classical OEFDR.

Dynamic signatures of the transition from stacking disordered to hexagonal ice: Dielectric and nuclear magnetic resonance studies

NASA Astrophysics Data System (ADS)

Gainaru, C.; Vynokur, E.; Köster, K. W.; Fuentes-Landete, V.; Spettel, N.; Zollner, J.; Loerting, T.; Böhmer, R.

2018-04-01

Using various temperature-cycling protocols, the dynamics of ice I were studied via dielectric spectroscopy and nuclear magnetic resonance relaxometry on protonated and deuterated samples obtained by heating high-density amorphous ices as well as crystalline ice XII. Previous structural studies of ice I established that at temperatures of about 230 K, the stacking disorder of the cubic/hexagonal oxygen lattice vanishes. The present dielectric and nuclear magnetic resonance investigations of spectral changes disclose that the memory of the existence of a precursor phase is preserved in the hydrogen matrix up to 270 K. This finding of hydrogen mobility lower than that of the undoped hexagonal ice near the melting point highlights the importance of dynamical investigations of the transitions between various ice phases and sheds new light on the dynamics in ice I in general.

Diffusion and the dynamics of displacive phase transitions in cryolite (Na3AlF6) and chiolite (Na5Al3F14): Multi-nuclear NMR studies

NASA Astrophysics Data System (ADS)

Spearing, Dane R.; Stebbins, Jonathan F.; Farnan, Ian

1994-10-01

Cryolite is a mixed-cation perovskite (Na2(NaAl)F6) which undergoes a monoclinic to orthorhombic displacive phase transition at ˜550° C. Chiolite (Na5Al3F14) is associated with cryolite in natural deposits, and consists of sheets of corner sharing [AlF6] octahedra interlayered with edge-sharing [NaF6] octahedra. Multi-nuclear NMR line shape and relaxation time (T1) studies were performed on cryolite and chiolite in order to gain a better understanding of the atomic motions associated with the phase transition in cryolite, and Na diffusion in cryolite and chiolite. 27Al, 23Na, and 19F static NMR spectra and T1's in cryolite suggest that oscillatory motions of the [AlF6] octahedra among four micro-twin and anti-phase domains in α-cryolite begin at least 150° C below the transition temperature and persist above it. Variable temperature 23Na MAS NMR further indicates diffusional exchange at a rate of at least 13 kHz between the Na sites by the time the transition temperature is reached. 27Al and 23Na T1's show the same behavior with increasing temperature, indicating the same relaxation mechanisms are responsible for both. The first order nature of the cryolite transition is apparent as a jump in the 23Na and 27Al T1's. Above the transition temperature, the T1's decrease slightly indicating that the motions responsible for the drop in T1, are still present above the transition, further supporting the dynamic nature of the high temperature phase of cryolite. Chiolite 23Na static spectra decrease in linewidth with increasing temperature, indicating increased Na diffusion, which is interpreted as occurring within the [NaF6] sheets in the chiolite structure, but not between the two different Na sites. 27Al and 23Na T1's show similar behavior as in cryolite, but there is no discontinuity due to a phase transition. 19F T1's are constant from room temperature to 150° C indicating no oscillatory motion of the [AlF6] octahedra in chiolite.

Dynamic transport study of the plasmas with transport improvement in LHD and JT-60U

NASA Astrophysics Data System (ADS)

Ida, K.; Sakamoto, Y.; Inagaki, S.; Takenaga, H.; Isayama, A.; Matsunaga, G.; Sakamoto, R.; Tanaka, K.; Ide, S.; Fujita, T.; Funaba, H.; Kubo, S.; Yoshinuma, M.; Shimozuma, T.; Takeiri, Y.; Ikeda, K.; Michael, C.; Tokuzawa, T.; LHD experimental Group; JT-60 Team

2009-01-01

Transport analysis during the transient phase of heating (a dynamic transport study) applied to the plasma with internal transport barriers (ITBs) in the Large Helical Device (LHD) heliotron and the JT-60U tokamak is described. In the dynamic transport study the time of transition from the L-mode plasma to the ITB plasma is clearly determined by the onset of flattening of the temperature profile in the core region and a spontaneous phase transition from a zero curvature ITB (hyperbolic tangent shaped ITB) or a positive curvature ITB (concaved shaped ITB) to a negative curvature ITB (convex shaped ITB) and its back-transition are observed. The flattening of the core region of the ITB transition and the back-transition between a zero curvature ITB and a convex ITB suggest the strong interaction of turbulent transport in space.

Molecular dynamics simulation of shock-wave loading of copper and titanium

NASA Astrophysics Data System (ADS)

Bolesta, A. V.; Fomin, V. M.

2017-10-01

At extreme pressures and temperatures common materials form new dense phases with compacted atomic arrangements. By classical molecular dynamics simulation we observe that FCC copper undergo phase transformation to BCC structure. The transition occurs under shock wave loading at the pressures above 80 GPa and corresponding temperatures above 2000 K. We calculate phase diagram, show that at these pressures and low temperature FCC phase of copper is still stable and discuss the thermodynamic reason for phase transformation at high temperature shock wave regime. Titanium forms new hexagonal phase at high pressure as well. We calculate the structure of shock wave in titanium and observe that shock front splits in three parts: elastic, plastic and phase transformation. The possibility of using a phase transition behind a shock wave with further unloading for designing nanocrystalline materials with a reduced grain size is also shown.

Yield and Failure Behavior Investigated for Cross-Linked Phenolic Resins Using Molecular Dynamics

NASA Technical Reports Server (NTRS)

Monk, Joshua D.; Lawson, John W.

2016-01-01

Molecular dynamics simulations were conducted to fundamentally evaluate the yield and failure behavior of cross-linked phenolic resins at temperatures below the glass transition. Yield stress was investigated at various temperatures, strain rates, and degrees of cross-linking. The onset of non-linear behavior in the cross-linked phenolic structures was caused by localized irreversible molecular rearrangements through the rotation of methylene linkers followed by the formation or annihilation of neighboring hydrogen bonds. The yield stress results, with respect to temperature and strain rate, could be fit by existing models used to describe yield behavior of amorphous glasses. The degree of cross-linking only indirectly influences the maximum yield stress through its influence on glass transition temperature (Tg), however there is a strong relationship between the degree of cross-linking and the failure mechanism. Low cross-linked samples were able to separate through void formation, whereas the highly cross-linked structures exhibited bond scission.

Onset of Cooperative Dynamics in an Equilibrium Glass-Forming Metallic Liquid

DOE PAGES

Jaiswal, Abhishek; O’Keeffe, Stephanie; Mills, Rebecca; ...

2016-01-22

Onset of cooperative dynamics has been observed in many molecular liquids, colloids, and granular materials in the metastable regime on approaching their respective glass or jamming transition points, and is considered to play a significant role in the emergence of the slow dynamics. However, the nature of such dynamical cooperativity remains elusive in multicomponent metallic liquids characterized by complex many-body interactions and high mixing entropy. Herein, we report evidence of onset of cooperative dynamics in an equilibrium glass-forming metallic liquid (LM601: Zr 51Cu 36Ni 4Al 9). This is revealed by deviation of the mean effective diffusion coefficient from its high-temperaturemore » Arrhenius behavior below T A ≈ 1300 K, i.e., a crossover from uncorrelated dynamics above T A to landscape-influenced correlated dynamics below T A. Moreover, the onset/ crossover temperature T A in such a multicomponent bulk metallic glass-forming liquid is observed at approximately twice of its calorimetric glass transition temperature (T g ≈ 697 K) and in its stable liquid phase, unlike many molecular liquids.« less

Vibrations and reorientations of H2O molecules in [Sr(H2O)6]Cl2 studied by Raman light scattering, incoherent inelastic neutron scattering and proton magnetic resonance.

PubMed

Hetmańczyk, Joanna; Hetmańczyk, Lukasz; Migdał-Mikuli, Anna; Mikuli, Edward; Florek-Wojciechowska, Małgorzata; Harańczyk, Hubert

2014-04-24

Vibrational-reorientational dynamics of H2O ligands in the high- and low-temperature phases of [Sr(H2O)6]Cl2 was investigated by Raman Spectroscopy (RS), proton magnetic resonance ((1)H NMR), quasielastic and inelastic incoherent Neutron Scattering (QENS and IINS) methods. Neutron powder diffraction (NPD) measurements, performed simultaneously with QENS, did not indicated a change of the crystal structure at the phase transition (detected earlier by differential scanning calorimetry (DSC) at TC(h)=252.9 K (on heating) and at TC(c)=226.5K (on cooling)). Temperature dependence of the full-width at half-maximum (FWHM) of νs(OH) band at ca. 3248 cm(-1) in the RS spectra indicated small discontinuity in the vicinity of phase transition temperature, what suggests that the observed phase transition may be associated with a change of the H2O reorientational dynamics. However, an activation energy value (Ea) for the reorientational motions of H2O ligands in both phases is nearly the same and equals to ca. 8 kJ mol(-1). The QENS peaks, registered for low temperature phase do not show any broadening. However, in the high temperature phase a small QENS broadening is clearly visible, what implies that the reorientational dynamics of H2O ligands undergoes a change at the phase transition. (1)H NMR line is a superposition of two powder Pake doublets, differentiated by a dipolar broadening, suggesting that there are two types of the water molecules in the crystal lattice of [Sr(H2O)6]Cl2 which are structurally not equivalent average distances between the interacting protons are: 1.39 and 1.18 Å. However, their reorientational dynamics is very similar (τc=3.3⋅10(-10) s). Activation energies for the reorientational motion of these both kinds of H2O ligands have nearly the same values in an experimental error limit: and equal to ca. 40 kJ mole(-1). The phase transition is not seen in the (1)H NMR spectra temperature dependencies. Infrared (IR), Raman (RS) and inelastic incoherent neutron scattering (IINS) spectra were calculated by the DFT method and quite a good agreement with the experimental data was obtained. Copyright © 2014 Elsevier B.V. All rights reserved.

Anelasticity maps for acoustic dissipation associated with phase transitions in minerals

NASA Astrophysics Data System (ADS)

Carpenter, Michael A.; Zhang, Zhiying

2011-07-01

Acoustic dissipation due to structural phase transitions in minerals could give rise to large seismic attenuation effects superimposed on the high temperature background contribution from dislocations and grain boundaries in the Earth. In addition to the possibility of a sharp peak actually at a transition point for both compressional and shear waves, significant attenuation might arise over wider temperature intervals due to the mobility of transformation twins or other defects associated with the transition. Attenuation due to structural phase transitions in quartz, pyroxenes, perovskites, stishovite and hollandite, or to spin state transitions of Fe2+ in magnesiowüstite and perovskite and the hcp/bcc transition in iron-nickel (Fe-Ni) alloy, are reviewed from this perspective. To these can be added possible loss behaviour associated with reconstructive transitions which might occur by a ledge mechanism on topotactic interfaces (orthopyroxene/clinopyroxene, olivine/spinel and perovskite/postperovskite), with impurities (Snoek effect) or with mobility of protons. There are experimental difficulties associated with measuring dissipation effects in situ at simultaneous high pressures and temperatures, so reliance is currently placed on investigation of analogue phases such as LaCoO3 for spin-state behaviour and LaAlO3 for the dynamics of ferroelastic twin walls. Similarly, it is not possible to measure loss dynamics simultaneously at the low stresses and low frequencies that pertain in seismic waves, so reliance must be placed on combining different techniques, such as dynamic mechanical analysis (low frequency, relatively high stress) and resonant ultrasound spectroscopy (high frequency, low stress), to extrapolate acoustic loss behaviour over wide frequency, temperature and stress intervals. In this context 'anelasticity maps' provide a convenient means of representing different loss mechanisms. Contouring of the inverse mechanical quality factor, Q-1, can be achieved if the appropriate constitutive laws are known. The overall approach is illustrated using the examples of spin-state transitions of Co3+ in LaCoO3 and twin mobility in single crystals of the rhombohedral phase of LaAlO3. Anelasticity maps of this type should give seismologists a clearer view of the characteristic patterns of seismic velocity and attenuation that could be used to detect (or rule out) the presence of particular phase transitions or loss behaviour in the core and mantle.

Dynamics of Mantle Plume Controlled by both Post-spinel and Post-garnet Phase Transitions

NASA Astrophysics Data System (ADS)

Liu, H.; Leng, W.

2017-12-01

Mineralogical studies indicate that two major phase transitions occur near 660 km depth in the Earth's pyrolitic mantle: the ringwoodite (Rw) to perovskite (Pv) + magnesiowüstite (Mw) and majorite (Mj) to perovskite (Pv) phase transitions. Seismological results also show a complicated phase boundary structure for plume regions at this depth, including broad pulse, double reflections and depressed 660 km discontinuity beneath hot regions etc… These observations have been attributed to the co-existence of these two phase transformations. However, previous geodynamical modeling mainly focused on the effects of Rw-Pv+Mw phase transition on the plume dynamics and largely neglected the effects of Mj-Pv phase transition. Here we develop a 3-D regional spherical geodynamic model to study the influence of the combination of Rw - Pv+Mw and Mj - Pv phase transitions on plume dynamics, including the topography fluctuation of 660 km discontinuity, plume shape and penetration capability of plume. Our results show that (1) a double phase boundary occurs at the hot center area of plume while for other regions with relatively lower temperature the phase boundary is single and flat, which respectively corresponds to the double reflections in the seismic observations and a high velocity prism-like structure at the top of 660 km discontinuity; (2) a large amount of low temperature plume materials could be trapped to form a complex trapezoid overlying the 660 km depth; (3) Mj - Pv phase change strongly enhances the plume penetration capability at 660 km depth, which significantly increases the plume mass flux due to the increased plume radius, but significantly reduces plume heat flux due to the decreased plume temperature in the upper mantle. Our model results provide new enlightenments for better constraining seismic structure and mineral reactions at 660 km phase boundaries.

Mapping the temperature-dependent conformational landscapes of the dynamic enzymes cyclophilin A and urease

NASA Astrophysics Data System (ADS)

Thorne, Robert; Keedy, Daniel; Warkentin, Matthew; Fraser, James; Moreau, David; Atakisi, Hakan; Rau, Peter

Proteins populate complex, temperature-dependent ensembles of conformations that enable their function. Yet in X-ray crystallographic studies, roughly 98% of structures have been determined at 100 K, and most refined to only a single conformation. A combination of experimental methods enabled by studies of ice formation and computational methods for mining low-density features in electron density maps have been applied to determine the evolution of the conformational landscapes of the enzymes cyclophilin A and urease between 300 K and 100 K. Minority conformations of most side chains depopulate on cooling from 300 to ~200 K, below which subsequent conformational evolution is quenched. The characteristic temperatures for this depopulation are highly heterogeneous throughout each enzyme. The temperature-dependent ensemble of the active site flap in urease has also been mapped. These all-atom, site-resolved measurements and analyses rule out one interpretation of the protein-solvent glass transition, and give an alternative interpretation of a dynamical transition identified in site-averaged experiments. They demonstrate a powerful approach to structural characterization of the dynamic underpinnings of protein function. Supported by NSF MCB-1330685.

Mobility restrictions and glass transition behaviour of an epoxy resin under confinement.

PubMed

Djemour, A; Sanctuary, R; Baller, J

2015-04-07

Confinement can have a big influence on the dynamics of glass formers in the vicinity of the glass transition. Already 40 to 50 K above the glass transition temperature, thermal equilibration of glass formers can be strongly influenced by the confining substrate. We investigate the linear thermal expansion and the specific heat capacity cp of an epoxy resin (diglycidyl ether of bisphenol A, DGEBA) in a temperature interval of 120 K around the glass transition temperature. The epoxy resin is filled into controlled pore glasses with pore diameters between 4 and 111 nm. Since DGEBA can form H-bonds with silica surfaces, we also investigate the influence of surface silanization of the porous substrates. In untreated substrates a core/shell structure of the epoxy resin can be identified. The glass transition behaviours of the bulk phase and that of the shell phase are different. In silanized substrates, the shell phase disappears. At a temperature well above the glass transition, a second transition is found for the bulk phase - both in the linear expansion data as well as in the specific heat capacity. The cp data do not allow excluding the glass transition of a third phase as being the cause for this transition, whereas the linear expansion data do so. The additional transition temperature is interpreted as a separation between two regimes: above this temperature, macroscopic flow of the bulk phase inside the porous structure is possible to balance the mismatch of thermal expansion coefficients between DGEBA and the substrate. Below the transition temperature, this degree of freedom is hindered by geometrical constraints of the porous substrates. Moreover, this second transition could also be found in the linear expansion data of the shell phase.

Generalization of soft phonon modes

NASA Astrophysics Data System (ADS)

Rudin, Sven P.

2018-04-01

Soft phonon modes describe a collective movement of atoms that transform a higher-symmetry crystal structure into a lower-symmetry crystal structure. Such structural transformations occur at finite temperatures, where the phonons (i.e., the low-temperature vibrational modes) and the static perfect crystal structures provide an incomplete picture of the dynamics. Here, principal vibrational modes (PVMs) are introduced as descriptors of the dynamics of a material system with N atoms. The PVMs represent the independent collective movements of the atoms at a given temperature. Molecular dynamics (MD) simulations, here in the form of quantum MD using density functional theory calculations, provide both the data describing the atomic motion and the data used to construct the PVMs. The leading mode, PVM0, represents the 3 N -dimensional direction in which the system moves with greatest amplitude. For structural phase transitions, PVM0 serves as a generalization of soft phonon modes. At low temperatures, PVM0 reproduces the soft phonon mode in systems where one phonon dominates the phase transformation. In general, multiple phonon modes combine to describe a transformation, in which case PVM0 culls these phonon modes. Moreover, while soft phonon modes arise in the higher-symmetry crystal structure, PVM0 can be equally well calculated on either side of the structural phase transition. Two applications demonstrate these properties: first, transitions into and out of bcc titanium, and, second, the two crystal structures proposed for the β phase of uranium, the higher-symmetry structure of which stabilizes with temperature.

Role of entropy and structural parameters in the spin-state transition of LaCoO3

NASA Astrophysics Data System (ADS)

Chakrabarti, Bismayan; Birol, Turan; Haule, Kristjan

2017-11-01

The spin-state transition in LaCoO3 has eluded description for decades despite concerted theoretical and experimental effort. In this study, we approach this problem using fully charge self-consistent density functional theory + embedded dynamical mean field theory (DFT+DMFT). We show from first principles that LaCoO3 cannot be described by a single, pure spin state at any temperature. Instead, we observe a gradual change in the population of higher-spin multiplets with increasing temperature, with the high-spin multiplets being excited at the onset of the spin-state transition followed by the intermediate-spin multiplets being excited at the metal-insulator-transition temperature. We explicitly elucidate the critical role of lattice expansion and oxygen octahedral rotations in the spin-state transition. We also reproduce, from first principles, that the spin-state transition and the metal-insulator transition in LaCoO3 occur at different temperature scales. In addition, our results shed light on the importance of electronic entropy in driving the spin-state transition, which has so far been ignored in all first-principles studies of this material.

Theory of dynamic barriers, activated hopping, and the glass transition in polymer melts

NASA Astrophysics Data System (ADS)

Schweizer, Kenneth S.; Saltzman, Erica J.

2004-07-01

A statistical mechanical theory of collective dynamic barriers, slow segmental relaxation, and the glass transition of polymer melts is developed by combining, and in some aspects extending, methods of mode coupling, density functional, and activated hopping transport theories. A coarse-grained description of polymer chains is adopted and the melt is treated as a liquid of segments. The theory is built on the idea that collective density fluctuations on length scales considerably longer than the local cage scale are of primary importance in the deeply supercooled regime. The barrier hopping or segmental relaxation time is predicted to be a function primarily of a single parameter that is chemical structure, temperature, and pressure dependent. This parameter depends on the material-specific dimensionless amplitude of thermal density fluctuations (compressibility) and a reduced segmental density determined by the packing length and backbone characteristic ratio. Analytic results are derived for a crossover temperature Tc, collective barrier, and glass transition temperature Tg. The relation of these quantities to structural and thermodynamic properties of the polymer melt is established. A universal power-law scaling behavior of the relaxation time below Tc is predicted based on identification of a reduced temperature variable that quantifies the breadth of the supercooled regime. Connections between the ratio Tc/Tg, two measures of dynamic fragility, and the magnitude of the local relaxation time at Tg logically follow. Excellent agreement with experiment is found for these generic aspects, and the crucial importance of the experimentally observed near universality of the dynamic crossover time is established. Extensions of the theory to treat the full chain dynamics, heterogeneity, barrier fluctuations, and nonpolymeric thermal glass forming liquids are briefly discussed.

Concurrence of dynamical phase transitions at finite temperature in the fully connected transverse-field Ising model

NASA Astrophysics Data System (ADS)

Lang, Johannes; Frank, Bernhard; Halimeh, Jad C.

2018-05-01

We construct the finite-temperature dynamical phase diagram of the fully connected transverse-field Ising model from the vantage point of two disparate concepts of dynamical criticality. An analytical derivation of the classical dynamics and exact diagonalization simulations are used to study the dynamics after a quantum quench in the system prepared in a thermal equilibrium state. The different dynamical phases characterized by the type of nonanalyticities that emerge in an appropriately defined Loschmidt-echo return rate directly correspond to the dynamical phases determined by the spontaneous breaking of Z2 symmetry in the long-time steady state. The dynamical phase diagram is qualitatively different depending on whether the initial thermal state is ferromagnetic or paramagnetic. Whereas the former leads to a dynamical phase diagram that can be directly related to its equilibrium counterpart, the latter gives rise to a divergent dynamical critical temperature at vanishing final transverse-field strength.

Dynamic properties of the haptenic site of lipid haptens in phosphatidylcholine membranes. Their relation to the phase transition of the host lattice.

PubMed Central

Takeshita, K.; Utsumi, H.; Hamada, A.

1987-01-01

The relation between the dynamic properties of the haptenic site of lipid haptens and the phase transition of the host lattice was investigated using head group spin-labeled phosphatidylethanolamines, that is, spin-label lipid haptens (Brûlet, P., and H. M. McConnell, 1976, Proc. Natl. Acad. Sci. USA., 73:2977-2981; Brûlet, P., and H. M. McConnell, 1977, Biochemistry, 16:1209-1217). The electron spin resonance (ESR) spectra of the lipid haptens in liposomal membranes showed three narrow resonance lines, whose widths and hyperfine splitting values suggested that the haptenic site, i.e., the spin-label moiety, should be exposed in the water phase. The line width of each peak depended on the host lipid species and on the incubation temperature. A temperature study using dipalmitoylphosphatidylcholine (DPPC) liposomes showed that the dynamic properties of the haptenic site were related to the main phase transition and the subphase transition of the host lattice but not to the prephase transition. The angular amplitudes of the tumbling motion of the haptenic site were estimated using oriented multibilayer systems. The angular amplitude of dipalmitoyl-phosphatidyl-N-[[N-(1-oxyl-2,2,6, 6-tetramethyl-4-piperidinyl)-carbamoyl]-methyl]-ethanolamine in DPPC membranes was 63 degrees at 2 degrees C, and it increased slightly with an increase in temperature regardless of the phase transition of the host lattice. The value for egg phosphatidylcholine (PC) at 25 degrees C was the same as for DPPC above its main phase transition temperature. Rotational correlation time analysis showed that the axial rotation of the haptenic site was preferable to the tumbling motion of the rotational axis, and the predominance depended on the phase transition, Lc----L beta' and P beta'----L alpha. Elongation of the spacer arm between the haptenic site and phosphate increased the angular amplitude of the tumbling motion but reduced the effect of the host lattice. Spin-label lipid haptens with unsaturated fatty acyl chains were distributed heterogeneously in DPPC membranes, whereas those with the same fatty acyl chain as the host lattice were distributed randomly. The ESR spectrum of a lipid hapten under its prephase transition temperature showed two components, broad and narrow. This suggests that at least two different domains, a hapten-rich domain and a hapten-poor one, may coexist in membranes. ESR measurements at various temperatures suggested that the haptenic site fraction in the hapten-rich domain decreased in part during the phase transition from L beta' to P beta', and disappeared completely in the La phase. The spatial mobility and lateral diffusion of lipid haptens will be discussed in greater detail. PMID:2822160

Atmospheric circulation of extrasolar giant planets

NASA Astrophysics Data System (ADS)

Showman, A. P.

2012-12-01

Of the many known extrasolar planets, over 100 have orbital semi-major axes less than 0.1 AU, and a significant fraction of these hot Jupiters and Neptunes are known to transit their stars, allowing them to be characterized with the Spitzer, Hubble, and groundbased telescopes. The stellar flux incident on these planets is expected to drive an atmospheric circulation that shapes the day-night temperature difference, infrared light curves, spectra, albedo, and atmospheric composition, and recent Spitzer infrared light curves show evidence for dynamical meteorology in these planets' atmospheres. Here, I will survey basic dynamical ideas and detailed 3D numerical models that illuminate the atmospheric circulation of these exotic, tidally locked planets. These models suggest that, generally, the circulation will be characterized by broad, fast zonal jets, with day-night temperature contrasts at the photosphere that may vary from small in some cases to large in others. I will discuss the dynamical mechanisms for maintaining the fast zonal jets that develop in these models, as well as the mechanisms for controlling the temperature patterns, including the day-night temperature contrasts. These mechanisms help to explain current observations, and they predict regime transitions for how the wind and temperature patterns should vary with the incident stellar flux, strength of atmospheric drag, and other parameters. These transitions are observable and in some cases are already becoming evident in the data. I will also compare the circulation of the hot Jupiters to that of young, massive giant planets being directly imaged around other stars, which will be the subject of a new observational vanguard over the next decade. To emphasize the similarities as well as differences, I will ground this discussion in our understanding of the more familiar atmospheric dynamical regime of Earth, as well as our "local" giant planets Jupiter, Saturn, Uranus, and Neptune.

Atmospheric circulation of extrasolar giant planets

NASA Astrophysics Data System (ADS)

Showman, A. P.

2011-12-01

Of the many known extrasolar planets, nearly 200 have orbital semi-major axes less than 0.1 AU, and a significant fraction of these hot Jupiters and Neptunes are known to transit their stars, allowing them to be characterized with the Spitzer, Hubble, and groundbased telescopes. The stellar flux incident on these planets is expected to drive an atmospheric circulation that shapes the day-night temperature difference, infrared light curves, spectra, albedo, and atmospheric composition, and recent Spitzer infrared light curves show evidence for dynamical meteorology in these planets' atmospheres. Here, I will survey basic dynamical ideas and detailed 3D numerical models that illuminate the atmospheric circulation of these exotic, tidally locked planets. These models suggest that, generally, the circulation will be characterized by broad, fast zonal jets, with day-night temperature contrasts at the photosphere that may vary from small in some cases to large in others. I will discuss the dynamical mechanisms for maintaining the fast zonal jets that develop in these models, as well as the mechanisms for controlling the temperature patterns, including the day-night temperature contrasts. These mechanisms help to explain current observations, and they predict regime transitions for how the wind and temperature patterns should vary with the incident stellar flux, strength of atmospheric drag, and other parameters. These transitions are observable and in some cases are already becoming evident in the data. I will also compare the circulation of the hot Jupiters to that of young, massive giant planets being directly imaged around other stars, which will be the subject of a new observational vanguard over the next decade. To emphasize the similarities as well as differences, I will ground this discussion in our understanding of the more familiar atmospheric dynamical regime of Earth, as well as our "local" giant planets Jupiter, Saturn, Uranus, and Neptune.

Bio-inspired method to obtain multifunctional dynamic nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kushner, Aaron M.; Guan, Zhibin; Williams, Gregory

A method for a polymeric or nanocomposite material. The method includes assembling a multiphase hard-soft structure, where the structure includes a hard micro- or nano-phase, and a soft micro- or nano-phase that includes a polymeric scaffold. In the method, the polymeric scaffold includes dynamically interacting motifs and has a glass transition temperature (T.sub.g) lower than the intended operating temperature of the material.

Insight into structural phase transitions from the decoupled anharmonic mode approximation

NASA Astrophysics Data System (ADS)

Adams, Donat J.; Passerone, Daniele

2016-08-01

We develop a formalism (decoupled anharmonic mode approximation, DAMA) that allows calculation of the vibrational free energy using density functional theory even for materials which exhibit negative curvature of the potential energy surface with respect to atomic displacements. We investigate vibrational modes beyond the harmonic approximation and approximate the potential energy surface with the superposition of the accurate potential along each normal mode. We show that the free energy can stabilize crystal structures at finite temperatures which appear dynamically unstable at T  =  0. The DAMA formalism is computationally fast because it avoids statistical sampling through molecular dynamics calculations, and is in principle completely ab initio. It is free of statistical uncertainties and independent of model parameters, but can give insight into the mechanism of a structural phase transition. We apply the formalism to the perovskite cryolite, and investigate the temperature-driven phase transition from the P21/n to the Immm space group. We calculate a phase transition temperature between 710 and 950 K, in fair agreement with the experimental value of 885 K. This can be related to the underestimation of the interaction of the vibrational states. We also calculate the main axes of the thermal ellipsoid and can explain the experimentally observed increase of its volume for the fluorine by 200-300% throughout the phase transition. Our calculations suggest the appearance of tunneling states in the high temperature phase. The convergence of the vibrational DOS and of the critical temperature with respect of reciprocal space sampling is investigated using the polarizable-ion model.

Insight into structural phase transitions from the decoupled anharmonic mode approximation.

PubMed

Adams, Donat J; Passerone, Daniele

2016-08-03

We develop a formalism (decoupled anharmonic mode approximation, DAMA) that allows calculation of the vibrational free energy using density functional theory even for materials which exhibit negative curvature of the potential energy surface with respect to atomic displacements. We investigate vibrational modes beyond the harmonic approximation and approximate the potential energy surface with the superposition of the accurate potential along each normal mode. We show that the free energy can stabilize crystal structures at finite temperatures which appear dynamically unstable at T  =  0. The DAMA formalism is computationally fast because it avoids statistical sampling through molecular dynamics calculations, and is in principle completely ab initio. It is free of statistical uncertainties and independent of model parameters, but can give insight into the mechanism of a structural phase transition. We apply the formalism to the perovskite cryolite, and investigate the temperature-driven phase transition from the P21/n to the Immm space group. We calculate a phase transition temperature between 710 and 950 K, in fair agreement with the experimental value of 885 K. This can be related to the underestimation of the interaction of the vibrational states. We also calculate the main axes of the thermal ellipsoid and can explain the experimentally observed increase of its volume for the fluorine by 200-300% throughout the phase transition. Our calculations suggest the appearance of tunneling states in the high temperature phase. The convergence of the vibrational DOS and of the critical temperature with respect of reciprocal space sampling is investigated using the polarizable-ion model.

Complex conductance of ultrathin La 2-xSr xCuO 4 films and heterostructures

DOE PAGES

V. A. Gasparov; Bozovic, I.

2015-10-23

We used atomic-layer molecular beam epitaxy to synthesize bilayers of a cuprate metal (La 1.55Sr 0.45CuO 4) and a cuprate insulator (La 2CuO 4), in which each layer is just one unit cells thick. We have studied the magnetic field and temperature dependence of the complex sheet conductance, σ(ω), of these films. Experiments have been carried out at frequencies between 2 and 50 MHz using the single-spiral coil technique. We found that: (i) the inductive response starts at ΔT = 3 K lower temperatures than Re σ(T), which in turn is characterized by a peak close to the transition, (ii)more » this shift is almost constant with magnetic field up to 14 mT; (iii) ΔT increases sharply up to 4 K at larger fields and becomes constant up to 8 T; (iv) the vortexdiffusion constant D(T) is not linear with T at low temperatures as in the case of free vortices, but is rather exponential due to pinning of vortex cores, and (v) the dynamic Berezinski–Kosterlitz–Thouless (BKT) transition temperature occurs at the point where Y=(l ω/ξ+) 2 = 1. As a result, our experimental results can be described well by the extended dynamic theory of the BKT transition and dynamics of bound vortex–antivortex pairs with short separation lengths.« less

Body Temperature-Related Structural Transitions of Monotremal and Human Hemoglobin

PubMed Central

Digel, I.; Maggakis-Kelemen, Ch.; Zerlin, K. F.; Linder, Pt.; Kasischke, N.; Kayser, P.; Porst, D.; Temiz Artmann, A.; Artmann, G. M.

2006-01-01

In this study, temperature-related structural changes were investigated in human, duck-billed platypus (Ornithorhynchus anatinus, body temperature Tb = 31–33°C), and echidna (Tachyglossus aculeatus, body temperature Tb = 32–33°C) hemoglobin using circular dichroism spectroscopy and dynamic light scattering. The average hydrodynamic radius (Rh) and fractional (normalized) change in the ellipticity (Fobs) at 222 ± 2 nm of hemoglobin were measured. The temperature was varied stepwise from 25°C to 45°C. The existence of a structural transition of human hemoglobin at the critical temperature Tc between 36–37°C was previously shown by micropipette aspiration experiments, viscosimetry, and circular dichroism spectroscopy. Based on light-scattering measurements, this study proves the onset of molecular aggregation at Tc. In two different monotremal hemoglobins (echidna and platypus), the critical transition temperatures were found between 32–33°C, which are close to the species' body temperature Tb. The data suggest that the correlation of the structural transition's critical temperature Tc and the species' body temperature Tb is not mere coincidence but, instead, is a more widespread structural phenomenon possibly including many other proteins. PMID:16844747

Body temperature-related structural transitions of monotremal and human hemoglobin.

PubMed

Digel, I; Maggakis-Kelemen, Ch; Zerlin, K F; Linder, Pt; Kasischke, N; Kayser, P; Porst, D; Temiz Artmann, A; Artmann, G M

2006-10-15

In this study, temperature-related structural changes were investigated in human, duck-billed platypus (Ornithorhynchus anatinus, body temperature T(b) = 31-33 degrees C), and echidna (Tachyglossus aculeatus, body temperature T(b) = 32-33 degrees C) hemoglobin using circular dichroism spectroscopy and dynamic light scattering. The average hydrodynamic radius (R(h)) and fractional (normalized) change in the ellipticity (F(obs)) at 222 +/- 2 nm of hemoglobin were measured. The temperature was varied stepwise from 25 degrees C to 45 degrees C. The existence of a structural transition of human hemoglobin at the critical temperature T(c) between 36-37 degrees C was previously shown by micropipette aspiration experiments, viscosimetry, and circular dichroism spectroscopy. Based on light-scattering measurements, this study proves the onset of molecular aggregation at T(c). In two different monotremal hemoglobins (echidna and platypus), the critical transition temperatures were found between 32-33 degrees C, which are close to the species' body temperature T(b). The data suggest that the correlation of the structural transition's critical temperature T(c) and the species' body temperature T(b) is not mere coincidence but, instead, is a more widespread structural phenomenon possibly including many other proteins.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anand, Sampurn; Mohanty, Subhendra; Dey, Ujjal Kumar, E-mail: sampurn@prl.res.in, E-mail: ujjal@cts.iitkgp.ernet.in, E-mail: mohanty@prl.res.in

Cosmological phase transitions can be a source of Stochastic Gravitational Wave (SGW) background. Apart from the dynamics of the phase transition, the characteristic frequency and the fractional energy density Ω{sub gw} of the SGW depends upon the temperature of the transition. In this article, we compute the SGW spectrum in the light of QCD equation of state provided by the lattice results. We find that the inclusion of trace anomaly from lattice QCD, enhances the SGW signal generated during QCD phase transition by ∼ 50% and the peak frequency of the QCD era SGW are shifted higher by ∼ 25%more » as compared to the earlier estimates without trace anomaly. This result is extremely significant for testing the phase transition dynamics near QCD epoch.« less

Orientation dynamics in isotropic phases of model oligofluorenes: glass or liquid crystal.

PubMed

Somma, E; Chi, C; Loppinet, B; Grinshtein, J; Graf, R; Fytas, G; Spiess, H W; Wegner, G

2006-05-28

Orientation molecular dynamics were investigated in a series of "defect-free" oligofluorenes by depolarized dynamic light scattering and dynamic NMR spectroscopy. Typical liquid crystalline pretransitional dynamics were observed upon cooling the isotropic phase to the liquid crystalline phase with strong increase of the scattered intensity and slowing down of the characteristic time of the probed collective relaxation. This is well accounted for by the Landau-de Gennes theory, however, with a strong temperature dependence of the viscosity coefficient, reflecting the proximity of the glass transition. For the trimer the two transitions almost overlap and the molecular orientation coincide with the alpha-relaxation associated with the glass transition. The NMR measurements confirm that the time scale of the dynamics is completely governed by the glass process, yet the geometry of the motion is anisotropic, yielding order parameters ranging from 0.15 to 0.25 for the long axis in the liquid crystalline phase. The glass transition is therefore geometrically restricted with poorly ordered mesophase which is consistent with the weak transverse phonons in the light scattering experiment down to Tg+20 K.

Lattice dynamics of a rotor-stator molecular crystal: Fullerene-cubane C60ṡC8H8

NASA Astrophysics Data System (ADS)

Bousige, Colin; Rols, Stéphane; Cambedouzou, Julien; Verberck, Bart; Pekker, Sándor; Kováts, Éva; Durkó, Gábor; Jalsovsky, István; Pellegrini, Éric; Launois, Pascale

2010-11-01

The dynamics of fullerene-cubane (C60ṡC8H8) cocrystal is studied combining experimental [x-ray diffuse scattering, quasielastic and inelastic neutron scattering (INS)] and simulation (molecular dynamics) investigations. Neutron scattering gives direct evidence of the free rotation of fullerenes and of the libration of cubanes in the high-temperature phase, validating the “rotor-stator” description of this molecular system. X-ray diffuse scattering shows that orientational disorder survives the order/disorder transition in the low-temperature phase, although the loss of fullerene isotropic rotational diffusion is featured by the appearance of a 2.2 meV mode in the INS spectra. The coupling between INS and simulations allows identifying a degeneracy lift of the cubane librations in the low temperature phase, which is used as a tool for probing the environment of cubane in this phase and for getting further insights into the phase transition mechanism.

Influence of long-time stress relief treatments on the dynamic fracture toughness properties of ASME SA508 C1 2a and ASME SA533 GR B C12 pressure vessel steels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Logsdon, W.A.

1982-03-01

Dynamic fracture toughness tests were performed on materials which had been subjected to one of three long-time post weld type stress relief heat treatments: 48 hours at 1000/degree/F (538/degree/C), 24 hours at 1125/degree/F (607/degree/C), and 48 hours at 1125/degree/F (607/degree/C). Linear elastic K/sub Id/ results were obtained at low temperatures while J-integral techniques were utilized to evaluate dynamic fracture toughness over the transition and upper shelf temperature ranges. Tensile, Charpy impact, and drop weight nil-ductility transition tests as well as room temperature, air environment fatigue crack growth rate tests (SA508 Cl 2a only) were also performed. The fracture toughness ofmore » both materials exceeded the ASME specified minimum reference toughness K/sub IR/ curve. 17 refs.« less

Water Hydrogen-Bonding Network Structure and Dynamics at Phospholipid Multibilayer Surface: Femtosecond Mid-IR Pump-Probe Spectroscopy.

PubMed

Kundu, Achintya; Błasiak, Bartosz; Lim, Joon-Hyung; Kwak, Kyungwon; Cho, Minhaeng

2016-03-03

The water hydrogen-bonding network at a lipid bilayer surface is crucial to understanding membrane structures and its functional activities. With a phospholipid multibilayer mimicking a biological membrane, we study the temperature dependence of water hydrogen-bonding structure, distribution, and dynamics at a lipid multibilayer surface using femtosecond mid-IR pump-probe spectroscopy. We observe two distinguished vibrational lifetime components. The fast component (0.6 ps) is associated with water interacting with a phosphate part, whereas the slow component (1.9 ps) is with bulk-like choline-associated water. With increasing temperature, the vibrational lifetime of phosphate-associated water remains constant though its relative fraction dramatically increases. The OD stretch vibrational lifetime of choline-bound water slows down in a sigmoidal fashion with respect to temperature, indicating a noticeable change of the water environment upon the phase transition. The water structure and dynamics are thus shown to be in quantitative correlation with the structural change of liquid multibilayer upon the gel-to-liquid crystal phase transition.

Ab initio molecular dynamic study of solid-state transitions of ammonium nitrate

PubMed Central

Yu, Hongyu; Duan, Defang; Liu, Hanyu; Yang, Ting; Tian, Fubo; Bao, Kuo; Li, Da; Zhao, Zhonglong; Liu, Bingbing; Cui, Tian

2016-01-01

High-pressure polymorphism and phase transitions have wide ranging consequences on the basic properties of ammonium nitrate. However, the phase diagram of ammonium nitrate at high pressure and high temperature is still under debate. This study systematically investigates the phase transitions and structural properties of ammonium nitrate at a pressure range of 5–60 GPa and temperature range of 250–400 K by ab initio molecular dynamics simulations. Two new phases are identified: one corresponds to the experimentally observed phase IV’ and the other is named AN-X. Simultaneously, the lattice strains play a significant role in the formation and stabilization of phase IV’, providing a reasonable explanation for experimental observation of phase IV-IV’ transition which only appears under nonhydrostatic pressure. In addition, 12 O atoms neighboring the NH (N atom in ammonium cation) atom are selected as reference system to clearly display the tanglesome rotation of ammonium cation. PMID:26754622

Thermally Driven Electronic Topological Transition in FeTi

DOE PAGES

Yang, F. C.; Muñoz, J. A.; Hellman, O.; ...

2016-08-08

In this paper, ab initio molecular dynamics, supported by inelastic neutron scattering and nuclear resonant inelastic x-ray scattering, showed an anomalous thermal softening of the M 5 - phonon mode in B2-ordered FeTi that could not be explained by phonon-phonon interactions or electron-phonon interactions calculated at low temperatures. A computational investigation showed that the Fermi surface undergoes a novel thermally driven electronic topological transition, in which new features of the Fermi surface arise at elevated temperatures. Finally, the thermally induced electronic topological transition causes an increased electronic screening for the atom displacements in the M 5 - phonon mode andmore » an adiabatic electron-phonon interaction with an unusual temperature dependence.« less

Study of structural morphologies of thermoresponsive diblock AB and triblock BAB copolymers (A = poly(N-isopropylacrylamide), B = polystyrene)

NASA Astrophysics Data System (ADS)

Rodríguez-Hidalgo, María del Rosario; Soto-Figueroa, César; Vicente, Luis

2018-03-01

Structural morphologies of diblock AB and triblock BAB copolymers (A = poly(N-isopropylacrylamide), B = polystyrene) in aqueous environment have been investigated by dissipative particle dynamics (DPD). In triblock copolymers insoluble PS blocks contract while soluble pNIPAM blocks stay at the periphery forming looped chains as corona. As the temperature is increased there is a continuous morphological transition and micelles form ellipsoidal structures with segregated polymer zones. The phase transition of looped pNIPAM chains occurs at lower temperature than for linear chains and within broader temperature range. It is discussed how the chain topology of pNIPAM affects the phase transition.

Dual Transition Edge Sensor Bolometer for Enhanced Dynamic Range

NASA Technical Reports Server (NTRS)

Chervenak, J. A.; Benford, D. J.; Moseley, S. H.; Irwin, K. D.

2004-01-01

Broadband surveys at the millimeter and submillimeter wavelengths will require bolometers that can reach new limits of sensitivity and also operate under high background conditions. To address this need, we present results on a dual transition edge sensor (TES) device with two operating modes: one for low background, ultrasensitive detection and one for high background, enhanced dynamic range detection. The device consists of a detector element with two transition temperatures (T(sub c)) of 0.25 and 0.51 K located on the same micromachined, thermally isolated membrane structure. It can be biased on either transition, and features phonon-limited noise performance at the lower T(sub c). We measure noise performance on the lower transition 7 x 10(exp -18) W/rt(Hz) and the bias power on the upper transition of 12.5 pW, giving a factor of 10 enhancement of the dynamic range for the device. We discuss the biasable range of this type of device and present a design concept to optimize utility of the device.

Role of Entropy and Structural Parameters in the Spin State Transition of LaCoO3

NASA Astrophysics Data System (ADS)

Chakrabarti, Bismayan; Birol, Turan; Haule, Kristjan

The spin state transition in LaCoO3 has eluded description for decades despite concerted theoretical and experimental effort. In this study, we approach this problem using fully charge consistent Density Functional Theory + Dynamical Mean Field Theory (DFT+DMFT). We show, from first principles, that LaCoO3 cannot be described by a single, pure spin state at any temperature, but instead shows a gradual change in the population of higher spin multiples as temperature is increased. We explicitly elucidate the critical role of the lattice expansion and oxygen octahedral rotations in the spin state transition. We also show that the spin state transition and the metal-insulator transition in the compound occur at different temperatures. In addition, our results shed light on the importance of electronic entropy, which has so far been ignored in all first principles studies of this material.

Ground state degeneracy, energy barriers, and molecular dynamics evidence for two-dimensional disorder in black phosphorus and monochalcogenide monolayers at finite temperature

NASA Astrophysics Data System (ADS)

Mehboudi, Mehrshad; Barraza-Lopez, Salvador; Dorio, Alex M.; Zhu, Wenjuan; van der Zande, Arend; Churchill, Hugh O. H.; Pacheco-Sanjuan, Alejandro A.; Harriss, Edmund O.; Kumar, Pradeep

Mono-layers of black phosphorus and other two dimensional materials such as mono-layers of SiSe, GeS, GeSe, GeTe, Sns, SnSe, and SnTe with a similar crystalline structure have a four-fold degenerate ground state that leads to two-dimensional disorder at finite temperature. Disorder happens when neighboring atoms gently re-accommodate bonds beyond a critical temperature. In this talk, the effect of atomic numbers on the transition temperature will be discussed. In addition Car-Parinello molecular dynamics calculations at temperatures 30, 300 and 1000 K were performed on supercells containing more than five hundred atoms and the results from these calculations confirm the transition onto a two-dimensional disordered structure past the critical temperature, which is close to room temperature for many of these compounds. References: M. Mehboudi, A.M. Dorio, W. Zhu, A. van der Zande, H.O.H. Churchill, A.A. Pacheco Sanjuan, E.O.H. Harris, P. Kumar, and S. Barraza-Lopez. arXiv:1510.09153.

Estimating Arrhenius parameters using temperature programmed molecular dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Imandi, Venkataramana; Chatterjee, Abhijit, E-mail: abhijit@che.iitb.ac.in

2016-07-21

Kinetic rates at different temperatures and the associated Arrhenius parameters, whenever Arrhenius law is obeyed, are efficiently estimated by applying maximum likelihood analysis to waiting times collected using the temperature programmed molecular dynamics method. When transitions involving many activated pathways are available in the dataset, their rates may be calculated using the same collection of waiting times. Arrhenius behaviour is ascertained by comparing rates at the sampled temperatures with ones from the Arrhenius expression. Three prototype systems with corrugated energy landscapes, namely, solvated alanine dipeptide, diffusion at the metal-solvent interphase, and lithium diffusion in silicon, are studied to highlight variousmore » aspects of the method. The method becomes particularly appealing when the Arrhenius parameters can be used to find rates at low temperatures where transitions are rare. Systematic coarse-graining of states can further extend the time scales accessible to the method. Good estimates for the rate parameters are obtained with 500-1000 waiting times.« less

Determination of the Glass-Transition Temperature of GRPS and CFRPS Using a Torsion Pendulum in Regimes of Freely Damped Vibrations and Quasi-Stastic Torsion of Specimens

NASA Astrophysics Data System (ADS)

Startsev, V. O.; Lebedev, M. P.; Molokov, M. V.

2018-03-01

A method to measure the glass-transition temperature of polymers and polymeric matrices of composite materials with the help of an inverse torsion pendulum over a wide range of temperatures is considered combining the method of free torsional vibrations and a quasi-static torsion of specimens. The glass-transition temperature Tg of a KMKS-1-80. T10 fiberglass, on increasing the frequency of freely damped torsional vibrations from 0.7 to 9.6 Hz, was found to increase from 132 to 140°C. The value of Tg of these specimens, determined by measuring the work of their torsion through a small fixed angle was 128.6°C ± 0.8°C. It is shown that the use of a torsion pendulum allows one to determine the glass-transition temperature of polymeric or polymer matrices of PCMs in dynamic and quasi-static deformation regimes of specimens.

Fundamental differences between glassy dynamics in two and three dimensions.

PubMed

Flenner, Elijah; Szamel, Grzegorz

2015-06-12

The two-dimensional freezing transition is very different from its three-dimensional counterpart. In contrast, the glass transition is usually assumed to have similar characteristics in two and three dimensions. Using computer simulations, here we show that glassy dynamics in supercooled two- and three-dimensional fluids are fundamentally different. Specifically, transient localization of particles on approaching the glass transition is absent in two dimensions, whereas it is very pronounced in three dimensions. Moreover, the temperature dependence of the relaxation time of orientational correlations is decoupled from that of the translational relaxation time in two dimensions but not in three dimensions. Last, the relationships between the characteristic size of dynamically heterogeneous regions and the relaxation time are very different in two and three dimensions. These results strongly suggest that the glass transition in two dimensions is different than in three dimensions.

Variational Flooding Study of a SN2 Reaction.

PubMed

Piccini, GiovanniMaria; McCarty, James J; Valsson, Omar; Parrinello, Michele

2017-02-02

We have studied the reaction dynamics of a prototypical organic reaction using a variationally optimized truncated bias to accelerate transitions between educt and product reactant states. The asymmetric S N 2 nucleophilic substitution reaction of fluoromethane and chloromethane CH 3 F + Cl - ⇌ CH 3 Cl + F - is considered, and many independent biased molecular dynamics simulations have been performed at 600, 900, and 1200 K, collecting several hundred transitions at each temperature. The transition times and relative rate constants have been obtained for both reaction directions. The activation energies extracted from an Arrhenius plot compare well with standard static calculations.

Enhancing pairwise state-transition weights: A new weighting scheme in simulated tempering that can minimize transition time between a pair of conformational states

NASA Astrophysics Data System (ADS)

Qiao, Qin; Zhang, Hou-Dao; Huang, Xuhui

2016-04-01

Simulated tempering (ST) is a widely used enhancing sampling method for Molecular Dynamics simulations. As one expanded ensemble method, ST is a combination of canonical ensembles at different temperatures and the acceptance probability of cross-temperature transitions is determined by both the temperature difference and the weights of each temperature. One popular way to obtain the weights is to adopt the free energy of each canonical ensemble, which achieves uniform sampling among temperature space. However, this uniform distribution in temperature space may not be optimal since high temperatures do not always speed up the conformational transitions of interest, as anti-Arrhenius kinetics are prevalent in protein and RNA folding. Here, we propose a new method: Enhancing Pairwise State-transition Weights (EPSW), to obtain the optimal weights by minimizing the round-trip time for transitions among different metastable states at the temperature of interest in ST. The novelty of the EPSW algorithm lies in explicitly considering the kinetics of conformation transitions when optimizing the weights of different temperatures. We further demonstrate the power of EPSW in three different systems: a simple two-temperature model, a two-dimensional model for protein folding with anti-Arrhenius kinetics, and the alanine dipeptide. The results from these three systems showed that the new algorithm can substantially accelerate the transitions between conformational states of interest in the ST expanded ensemble and further facilitate the convergence of thermodynamics compared to the widely used free energy weights. We anticipate that this algorithm is particularly useful for studying functional conformational changes of biological systems where the initial and final states are often known from structural biology experiments.

Enhancing pairwise state-transition weights: A new weighting scheme in simulated tempering that can minimize transition time between a pair of conformational states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiao, Qin, E-mail: qqiao@ust.hk; Zhang, Hou-Dao; Huang, Xuhui, E-mail: xuhuihuang@ust.hk

2016-04-21

Simulated tempering (ST) is a widely used enhancing sampling method for Molecular Dynamics simulations. As one expanded ensemble method, ST is a combination of canonical ensembles at different temperatures and the acceptance probability of cross-temperature transitions is determined by both the temperature difference and the weights of each temperature. One popular way to obtain the weights is to adopt the free energy of each canonical ensemble, which achieves uniform sampling among temperature space. However, this uniform distribution in temperature space may not be optimal since high temperatures do not always speed up the conformational transitions of interest, as anti-Arrhenius kineticsmore » are prevalent in protein and RNA folding. Here, we propose a new method: Enhancing Pairwise State-transition Weights (EPSW), to obtain the optimal weights by minimizing the round-trip time for transitions among different metastable states at the temperature of interest in ST. The novelty of the EPSW algorithm lies in explicitly considering the kinetics of conformation transitions when optimizing the weights of different temperatures. We further demonstrate the power of EPSW in three different systems: a simple two-temperature model, a two-dimensional model for protein folding with anti-Arrhenius kinetics, and the alanine dipeptide. The results from these three systems showed that the new algorithm can substantially accelerate the transitions between conformational states of interest in the ST expanded ensemble and further facilitate the convergence of thermodynamics compared to the widely used free energy weights. We anticipate that this algorithm is particularly useful for studying functional conformational changes of biological systems where the initial and final states are often known from structural biology experiments.« less

Superhigh moduli and tension-induced phase transition of monolayer gamma-boron at finite temperatures.

PubMed

Zhao, Junhua; Yang, Zhaoyao; Wei, Ning; Kou, Liangzhi

2016-03-16

Two dimensional (2D) gamma-boron (γ-B28) thin films have been firstly reported by the experiments of the chemical vapor deposition in the latest study. However, their mechanical properties are still not clear. Here we predict the superhigh moduli (785 ± 42 GPa at 300 K) and the tension-induced phase transition of monolayer γ-B28 along a zigzag direction for large deformations at finite temperatures using molecular dynamics (MD) simulations. The new phase can be kept stable after unloading process at these temperatures. The predicted mechanical properties are reasonable when compared with our results from density functional theory. This study provides physical insights into the origins of the new phase transition of monolayer γ-B28 at finite temperatures.

The spin-temperature theory of dynamic nuclear polarization and nuclear spin-lattice relaxation

NASA Technical Reports Server (NTRS)

Byvik, C. E.; Wollan, D. S.

1974-01-01

A detailed derivation of the equations governing dynamic nuclear polarization (DNP) and nuclear spin lattice relaxation by use of the spin temperature theory has been carried to second order in a perturbation expansion of the density matrix. Nuclear spin diffusion in the rapid diffusion limit and the effects of the coupling of the electron dipole-dipole reservoir (EDDR) with the nuclear spins are incorporated. The complete expression for the dynamic nuclear polarization has been derived and then examined in detail for the limit of well resolved solid effect transitions. Exactly at the solid effect transition peaks, the conventional solid-effect DNP results are obtained, but with EDDR effects on the nuclear relaxation and DNP leakage factor included. Explicit EDDR contributions to DNP are discussed, and a new DNP effect is predicted.

Molecular mobility of nematic E7 confined to molecular sieves with a low filling degree.

PubMed

Brás, A R; Frunza, S; Guerreiro, L; Fonseca, I M; Corma, A; Frunza, L; Dionísio, M; Schönhals, A

2010-06-14

The nematic liquid crystalline mixture E7 was confined with similar filling degrees to molecular sieves with constant composition but different pore diameters (from 2.8 to 6.8 nm). Fourier transform infrared analysis proved that the E7 molecules interact via the cyanogroup with the pore walls of the molecular sieves. The molecular dynamics of the system was investigated by broadband dielectric spectroscopy (10(-2)-10(9) Hz) covering a wide temperature range of approximately 200 K from temperatures well above the isotropic-nematic transition down to the glass transition of bulk E7. A variety of relaxation processes is observed including two modes that are located close to the bulk behavior in its temperature dependence. For all confined samples, two relaxation processes, at frequencies lower than the processes observed for the bulk, were detected. At lower temperatures, their relaxation rates have different temperature dependencies whereas at higher temperatures, they seem to collapse into one chart. The temperature dependence of the slowest process (S-process) obeys the Vogel-Fulcher-Tammann law indicating a glassy dynamics of the E7 molecules anchored to the pore surface. The pore size dependence of both the Vogel temperature and fragility revealed a steplike transition around 4 nm pore size, which indicates a transition from a strong to a fragile behavior. The process with a relaxation rate in between the bulklike and the S-process (I-process) shows no dependence on the pore size. The agreement of the I-process with the behavior of a 5CB surface layer adsorbed on nonporous silica leads to the assignment of E7 molecules anchored at the outer surface of the microcrystals of the molecular sieves.

Anomalously large isotope effect in the glass transition of water

DOE PAGES

Gainaru, Catalin; Agapov, Alexander L.; Fuentes-Landete, Violeta; ...

2014-11-24

Here we present the discovery of an unusually large isotope effect in the structural relaxation and the glass transition temperature T g of water. Dielectric relaxation spectroscopy of low-density as well as of vapor deposited amorphous water reveal T g differences of 10±2K between H 2O and D 2O, sharply contrasting with other hydrogen bonded liquids for which H/D exchange increases T g by typically less than 1K. We show that the large isotope effect and the unusual variation of relaxation times in water at low temperatures can be explained in terms of quantum effects. Thus, our findings shed newmore » light on water's peculiar low-temperature dynamics and the possible role of quantum effects in its structural relaxation, and possibly in dynamics of other low molecular weight liquids.« less

Unusual terahertz spectral weight and conductivity dynamics of the insulator-metal transition in Pr0.5Nd0.5NiO3 thin films

NASA Astrophysics Data System (ADS)

Santhosh Kumar, K.; Das, Sarmistha; Eswara Phanindra, V.; Rana, D. S.

2017-12-01

The metal-insulator transition (MIT) in correlated systems is a central phenomenon that possesses potential for several emerging technologies. We investigate the kinetics of such MIT in perovskite nickelates by studying the terahertz (THz) low-energy charge dynamics in orthorhombic and tetragonal symmetries of Pr0.5Nd0.5NiO3 thin films. The THz conductivity of the orthorhombic thin film is dominated by Drude behavior in the entire temperature range, albeit a dominant anomaly at and around the MIT region. The tetragonal thin film exhibits different overall THz conductivity dynamics though, i.e. of a Drude-Smith (DS) type in the entire temperature range, the DS coefficient signifying dominant backscattering peaks in the MIT region. While the overall THz dynamics profile is different for the two films, a unique yet similar sensitivity of the I-M transition regions of both films to THz frequencies underlines the fundamental origin of the bi-critical phase around MIT of the nickelates. The peculiar behavior around the I-M transition, as evaluated in the framework of a percolative path approximation based Dyre expression, emphasizes the importance of critical metallic volume fraction (f c) for the percolation conduction, as an f c of ~0.645 obtained for the present case, along with evidence for the absence of super-heating.

Phase transitions of sodium niobate powder and ceramics, prepared by solid state synthesis

NASA Astrophysics Data System (ADS)

Koruza, J.; Tellier, J.; Malič, B.; Bobnar, V.; Kosec, M.

2010-12-01

Phase transitions of sodium niobate, prepared by the solid state synthesis method, were examined using dielectric measurements, differential scanning calorimetry, and high temperature x-ray diffraction, in order to contribute to the clarification of its structural behavior below 400 °C. Four phase transitions were detected in the ceramic sample using dielectric measurements and differential scanning calorimetry and the obtained temperatures were in a good agreement with previous reports for the transitions of the P polymorph. The anomaly observed by dielectric measurements in the vicinity of 150 °C was frequency dependent and could be related to the dynamics of the ferroelectric nanoregions. The phase transitions of the as-synthesized NaNbO3 powder were investigated using differential scanning calorimetry and high temperature x-ray diffraction. The results show the existence of the Q polymorph at room temperature, not previously reported for the powder, which undergoes a transition to the R polymorph upon heating through a temperature region between 265 and 326.5 °C. This transition is mainly related to the displacement of Na into a more symmetric position and a minor change in the tilting system. The structures at room temperature, 250, 300, and 420 °C were refined by the Rietveld method and the evolution of the tilting system of the octahedral network and cationic displacement are reported.

Novel penta-graphene nanotubes: strain-induced structural and semiconductor–metal transitions

DOE PAGES

Wang, Zhanyu; Cao, Xinran; Qiao, Chong; ...

2017-11-17

Research into novel one-dimensional (1D) materials and associated structural transitions is of significant scientific interest. It is widely accepted that a 1D system with a short-range interaction cannot have 1D phase transition at finite temperature. In this paper, we propose a series of new stable carbon nanotubes by rolling up penta-graphene sheets, which exhibit fascinating well-defined 1D phase transitions triggered by axial strain. Our first-principles calculations show that such penta-graphene nanotubes (PGNTs) are dynamically stable by phonon calculations, but transform from a tri-layer structure to a highly defective single-walled nanotube at low temperature in molecular dynamics simulations. We show thatmore » moderate compressive strains can drive structural transitions of (4,4), (5,5), and (6,6) PGNTs, during which the distances of neighboring carbon dimers in the inner shell have a sudden drop, corresponding to dimer–dimer nonbonding to bonding transitions. After such transition, the tubes become much more thermally stable and undergo semiconductor–metal transitions under increasing strain. The band gaps of PGNTs are not sensitive to chirality whereas they can be tuned effectively from visible to short-wavelength infrared by appropriate strain, making them appealing materials for flexible nano-optoelectronics. In conclusion, these findings provide useful insight into unusual phase transitions in low-dimensional systems.« less

Novel penta-graphene nanotubes: strain-induced structural and semiconductor–metal transitions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zhanyu; Cao, Xinran; Qiao, Chong

Research into novel one-dimensional (1D) materials and associated structural transitions is of significant scientific interest. It is widely accepted that a 1D system with a short-range interaction cannot have 1D phase transition at finite temperature. In this paper, we propose a series of new stable carbon nanotubes by rolling up penta-graphene sheets, which exhibit fascinating well-defined 1D phase transitions triggered by axial strain. Our first-principles calculations show that such penta-graphene nanotubes (PGNTs) are dynamically stable by phonon calculations, but transform from a tri-layer structure to a highly defective single-walled nanotube at low temperature in molecular dynamics simulations. We show thatmore » moderate compressive strains can drive structural transitions of (4,4), (5,5), and (6,6) PGNTs, during which the distances of neighboring carbon dimers in the inner shell have a sudden drop, corresponding to dimer–dimer nonbonding to bonding transitions. After such transition, the tubes become much more thermally stable and undergo semiconductor–metal transitions under increasing strain. The band gaps of PGNTs are not sensitive to chirality whereas they can be tuned effectively from visible to short-wavelength infrared by appropriate strain, making them appealing materials for flexible nano-optoelectronics. In conclusion, these findings provide useful insight into unusual phase transitions in low-dimensional systems.« less

Glass transition dynamics and conductivity scaling in ionic deep eutectic solvents: The case of (acetamide + lithium nitrate/sodium thiocyanate) melts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tripathy, Satya N., E-mail: satyanarayantripathy@gmail.com; Wojnarowska, Zaneta; Knapik, Justyna

2015-05-14

A detailed investigation on the molecular dynamics of ionic deep eutectic solvents (acetamide + lithium nitrate/sodium thiocyanate) is reported. The study was carried out employing dielectric relaxation spectroscopy covering seven decades in frequency (10{sup −1}-10{sup 6} Hz) and in a wide temperature range from 373 K down to 173 K, accessing the dynamic observables both in liquid and glassy state. The dielectric response of the ionic system has been presented in the dynamic window of modulus formalism to understand the conductivity relaxation and its possible connection to the origin of localized motion. Two secondary relaxation processes appear below glass transitionmore » temperature. Our findings provide suitable interpretation on the nature of secondary Johari-Goldstein process describing the ion translation and orientation of dipoles in a combined approach using Ngai’s coupling model. A nearly constant loss feature is witnessed at shorter times/lower temperatures. We also discuss the ac conductivity scaling behavior using Summerfield approach and random free energy barrier model which establish the time-temperature superposition principle. These experimental observations have fundamental importance on theoretical elucidation of the conductivity relaxation and glass transition phenomena in molten ionic conductors.« less

Dynamic crossover in deeply cooled water confined in MCM-41 at 4 kbar and its relation to the liquid-liquid transition hypothesis

NASA Astrophysics Data System (ADS)

Wang, Zhe; Le, Peisi; Ito, Kanae; Leão, Juscelino B.; Tyagi, Madhusudan; Chen, Sow-Hsin

2015-09-01

With quasi-elastic neutron scattering, we study the single-particle dynamics of the water confined in a hydrophilic silica material, MCM-41, at 4 kbar. A dynamic crossover phenomenon is observed at 219 K. We compare this dynamic crossover with the one observed at ambient pressure and find that (a) above the crossover temperature, the temperature dependence of the characteristic relaxation time at ambient pressure exhibits a more evident super-Arrhenius behavior than that at 4 kbar. Especially, at temperatures below about 230 K, the relaxation time at 4 kbar is even smaller than that at ambient pressure. This feature is different from many other liquids. (b) Below the crossover temperature, the Arrhenius behavior found at ambient pressure has a larger activation energy compared to the one found at 4 kbar. We ascribe the former to the difference between the local structure of the low-density liquid (LDL) phase and that of the high-density liquid (HDL) phase, and the latter to the difference between the strength of the hydrogen bond of the LDL and that of the HDL. Therefore, we conclude that the phenomena observed in this paper are consistent with the LDL-to-HDL liquid-liquid transition hypothesis.

Dynamic crossover in deeply cooled water confined in MCM-41 at 4 kbar and its relation to the liquid-liquid transition hypothesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zhe; Le, Peisi; Ito, Kanae

With quasi-elastic neutron scattering, we study the single-particle dynamics of the water confined in a hydrophilic silica material, MCM-41, at 4 kbar. A dynamic crossover phenomenon is observed at 219 K. We compare this dynamic crossover with the one observed at ambient pressure and find that (a) above the crossover temperature, the temperature dependence of the characteristic relaxation time at ambient pressure exhibits a more evident super-Arrhenius behavior than that at 4 kbar. Especially, at temperatures below about 230 K, the relaxation time at 4 kbar is even smaller than that at ambient pressure. This feature is different from manymore » other liquids. (b) Below the crossover temperature, the Arrhenius behavior found at ambient pressure has a larger activation energy compared to the one found at 4 kbar. We ascribe the former to the difference between the local structure of the low-density liquid (LDL) phase and that of the high-density liquid (HDL) phase, and the latter to the difference between the strength of the hydrogen bond of the LDL and that of the HDL. Therefore, we conclude that the phenomena observed in this paper are consistent with the LDL-to-HDL liquid-liquid transition hypothesis.« less

Simulation studies of glassy nanoclusters

NASA Astrophysics Data System (ADS)

Bowles, Richard

2015-03-01

Glassy materials are amorphous solids usually formed by rapidly cooling a liquid below its equilibrium freezing temperature, trapping the particles in a liquid-like structure at the glass transition temperature. While appearing throughout nature and industry, these systems continue to challenge the way we think about the dynamics and thermodynamics of condensed matter and a fundamental understanding of the glass state remains elusive. This talk describes molecular simulation studies of glassy behaviour in binary Lennard-Jones nanoclusters. We show that the relaxation dynamics of the clusters is nonuniform and the core of the cluster goes through a glass transition at higher temperatures than at the surface. As the nanoclusters are cooled, they also exhibit a fragile-strong crossover in their dynamics and we explore how this phenomena is linked to the potential energy landscape of the clusters. Finally, we compare the properties of nanoclusters formed through vapour condensation, directly to the glassy state, with those of glassy clusters formed through traditional supercooling. The condensation clusters are shown to form ultra-stable glassy states analogous to the ultra-stable glasses formed by thin film vapour deposition onto a cold substrate. In all, our work suggests that nanoscale clusters exhibit some unique glassy features, while also offering potential insights into the fundamental nature of the glass transition.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kubo, Jisuke; Yamada, Masatoshi; Institut für Theoretische Physik, Universität Heidelberg,Philosophenweg 16, 69120 Heidelberg

We assume that the origin of the electroweak (EW) scale is a gauge-invariant scalar-bilinear condensation in a strongly interacting non-abelian gauge sector, which is connected to the standard model via a Higgs portal coupling. The dynamical scale genesis appears as a phase transition at finite temperature, and it can produce a gravitational wave (GW) background in the early Universe. We find that the critical temperature of the scale phase transition lies above that of the EW phase transition and below few O(100) GeV and it is strongly first-order. We calculate the spectrum of the GW background and find the scalemore » phase transition is strong enough that the GW background can be observed by DECIGO.« less

Some Correlations between Plate Shatter and Fracture Toughness.

DTIC Science & Technology

1987-02-01

temperatures. In this manner, any test for plate cracking should be akin to a Charpy test, where a series of notched test bars are broken over a...cracking under ballistic impact. The PSTT test is analogous to the transition temperature in a Charpy impact test, or to the nil ductility transition (NDT...210 C to -730 C. Standard Charpy specimens were machined from the plates and subsequently precracked in fatigue to about 2.5 mm and dynamically tested

Ferroelectric properties and polarization dynamics in Ba{sub 4}Sm{sub 2}Ti{sub 4}Ta{sub 6}O{sub 30} tungsten bronze ceramics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Xiao Li, E-mail: xiaolizi0618@zju.edu.cn; Chen, Xiang Ming

2016-04-11

Ferroelectricity and polarization reversal dynamics in Ba{sub 4}Sm{sub 2}Ti{sub 4}Ta{sub 6}O{sub 30} tungsten bronze ceramics were investigated by measuring dielectric spectra and the evolution of hysteresis loops over a wide temperature range. With decreasing temperature, the dielectric properties and differential scanning calorimetry results showed diffuse peaks at ∼280 K with large thermal hysteresis, suggesting a first order ferroelectric transition. A dielectric relaxation was observed at low temperature that followed the Vogel–Fulcher relationship. The saturation and remanent polarizations of the Ba{sub 4}Sm{sub 2}Ti{sub 4}Ta{sub 6}O{sub 30} ceramics showed remarkable dependence on the applied field and temperature. The temperature dependence of the coercivemore » field was divided into three linear regions and fitted to the Vopsaroiu model. Activation energies for polarization reversal of 0.73, 0.79, and 0.65 eV were determined for the following three regions: (I) the diffuse ferroelectric transition region (323.15–293.15 K), (II) the region just below the ferroelectric transition temperature (293.15–233.15 K), and (III) the low temperature relaxation region (233.15–173.15 K), respectively. The decrease of the activation energy in region III was attributed to the low temperature relaxation of Ba{sub 4}Sm{sub 2}Ti{sub 4}Ta{sub 6}O{sub 30}.« less

Hierarchical Biomolecular Dynamics: Picosecond Hydrogen Bonding Regulates Microsecond Conformational Transitions.

PubMed

Buchenberg, Sebastian; Schaudinnus, Norbert; Stock, Gerhard

2015-03-10

Biomolecules exhibit structural dynamics on a number of time scales, including picosecond (ps) motions of a few atoms, nanosecond (ns) local conformational transitions, and microsecond (μs) global conformational rearrangements. Despite this substantial separation of time scales, fast and slow degrees of freedom appear to be coupled in a nonlinear manner; for example, there is theoretical and experimental evidence that fast structural fluctuations are required for slow functional motion to happen. To elucidate a microscopic mechanism of this multiscale behavior, Aib peptide is adopted as a simple model system. Combining extensive molecular dynamics simulations with principal component analysis techniques, a hierarchy of (at least) three tiers of the molecule's free energy landscape is discovered. They correspond to chiral left- to right-handed transitions of the entire peptide that happen on a μs time scale, conformational transitions of individual residues that take about 1 ns, and the opening and closing of structure-stabilizing hydrogen bonds that occur within tens of ps and are triggered by sub-ps structural fluctuations. Providing a simple mechanism of hierarchical dynamics, fast hydrogen bond dynamics is found to be a prerequisite for the ns local conformational transitions, which in turn are a prerequisite for the slow global conformational rearrangement of the peptide. As a consequence of the hierarchical coupling, the various processes exhibit a similar temperature behavior which may be interpreted as a dynamic transition.

Prediction of glass transition temperature of freeze-dried formulations by molecular dynamics simulation.

PubMed

Yoshioka, Sumie; Aso, Yukio; Kojima, Shigeo

2003-06-01

To examine whether the glass transition temperature (Tg) of freeze-dried formulations containing polymer excipients can be accurately predicted by molecular dynamics simulation using software currently available on the market. Molecular dynamics simulations were carried out for isomaltodecaose, a fragment of dextran, and alpha-glucose, the repeated unit of dextran. in the presence or absence of water molecules. Estimated values of Tg were compared with experimental values obtained by differential scanning calorimetry (DSC). Isothermal-isobaric molecular dynamics simulations (NPTMD) and isothermal molecular dynamics simulations at a constant volume (NVTMD) were carried out using the software package DISCOVER (Material Studio) with the Polymer Consortium Force Field. Mean-squared displacement and radial distribution function were calculated. NVTMD using the values of density obtained by NPTMD provided the diffusivity of glucose-ring oxygen and water oxygen in amorphous alpha-glucose and isomaltodecaose, which exhibited a discontinuity in temperature dependence due to glass transition. Tg was estimated to be approximately 400K and 500K for pure amorphous a-glucose and isomaltodecaose, respectively, and in the presence of one water molecule per glucose unit, Tg was 340K and 360K, respectively. Estimated Tg values were higher than experimentally determined values because of the very fast cooling rates in the simulations. However, decreases in Tg on hydration and increases in Tg associated with larger fragment size could be demonstrated. The results indicate that molecular dynamics simulation is a useful method for investigating the effects of hydration and molecular weight on the Tg of lyophilized formulations containing polymer excipients. although the relationship between cooling rates and Tg must first be elucidated to predict Tg vales observed by DSC measurement. January 16.

Spatiotemporal dynamics of the spin transition in [Fe (HB(tz)3) 2] single crystals

NASA Astrophysics Data System (ADS)

Ridier, Karl; Rat, Sylvain; Shepherd, Helena J.; Salmon, Lionel; Nicolazzi, William; Molnár, Gábor; Bousseksou, Azzedine

2017-10-01

The spatiotemporal dynamics of the spin transition have been thoroughly investigated in single crystals of the mononuclear spin-crossover (SCO) complex [Fe (HB (tz )3)2] (tz = 1 ,2 ,4-triazol-1-yl) by optical microscopy. This compound exhibits an abrupt spin transition centered at 334 K with a narrow thermal hysteresis loop of ˜1 K (first-order transition). Most single crystals of this compound reveal exceptional resilience upon repeated switching (several hundred cycles), which allowed repeatable and quantitative measurements of the spatiotemporal dynamics of the nucleation and growth processes to be carried out. These experiments revealed remarkable properties of the thermally induced spin transition: high stability of the thermal hysteresis loop, unprecedented large velocities of the macroscopic low-spin/high-spin phase boundaries up to 500 µm/s, and no visible dependency on the temperature scan rate. We have also studied the dynamics of the low-spin → high-spin transition induced by a local photothermal excitation generated by a spatially localized (Ø = 2 μ m ) continuous laser beam. Interesting phenomena have been evidenced both in quasistatic and dynamic conditions (e.g., threshold effects and long incubation periods, thermal activation of the phase boundary propagation, stabilization of the crystal in a stationary biphasic state, and thermal cutoff frequency). These measurements demonstrated the importance of thermal effects in the transition dynamics, and they enabled an accurate determination of the thermal properties of the SCO compound in the framework of a simple theoretical model.

Molecular dynamics study of thermodynamic scaling of the glass-transition dynamics in ionic liquids over wide temperature and pressure ranges.

PubMed

Habasaki, J; Casalini, R; Ngai, K L

2010-03-25

Experimentally, superpositioning of dynamic properties such as viscosity, relaxation times, or diffusion coefficients under different conditions of temperature T, pressure P, and volume V by the scaling variable TV(gamma) (where gamma is a material constant) has been reported as a general feature of many kinds of glass-forming materials. In the present work, molecular dynamics (MD) simulations have been performed to study the scaling of dynamics near the glass-transition regime of ionic liquids. Scaling in the simulated 1-ethyl-3-methylimidazolium nitrate (EMIM-NO(3)) system has been tested over wide ranges of temperatures and pressures. TV(gamma) scaling of the dynamics is well described by master curves with gamma = 4.0 +/- 0.2 and 3.8 +/- 0.2 for cation and anion, respectively. Structures and Coulombic terms of the corresponding states are found to be quite similar. The temperature and pressure dependence of the pair correlation function show similar trends and therefore can be superpositioned onto the master curve. Although the behaviors with gamma = 4 might be expected from the relation, gamma = n/3, for the dynamics with the soft-core-type potential U = epsilon(sigma/r)(n), with n = 12, pair potentials used in the MD simulation have a more complex form, and not all the repulsive terms can play their roles in the heterogeneous structures determined by ion-ion interactions. Scaling is related to the common part of effective potentials related to the pair correlation functions, including the many-body effect in real space.

Dynamical heterogeneities of cold 2D Yukawa liquids

NASA Astrophysics Data System (ADS)

Wang, Kang; Huang, Dong; Feng, Yan

2018-06-01

Dynamical heterogeneities of 2D liquid dusty plasmas at different temperatures are investigated systematically using Langevin dynamical simulations. From the simulated trajectories, various heterogeneity measures have been calculated, such as the distance matrix, the averaged squared displacement, the non-Gaussian parameter, and the four-point susceptibility. It is found that, for 2D Yukawa liquids, both spatial and temporal heterogeneities in dynamics are more severe at a lower temperature near the melting point. For various temperatures, the calculated non-Gaussian parameter of 2D Yukawa liquids contains two peaks at different times, indicating the most heterogeneous dynamics, which are attributed to the transition of different motions and the α relaxation time, respectively. In the diffusive motion, the most heterogeneous dynamics for a colder Yukawa liquid happen more slowly, as indicated by both the non-Gaussian parameter and the four-point susceptibility.

Thermal transport dynamics in the quasi-single helicity state

NASA Astrophysics Data System (ADS)

McKinney, I. J.; Terry, P. W.

2017-06-01

A dynamical model describing oscillations between multiple and single helicity configurations in the quasi-single helicity (QSH) state of the reversed field pinch [P. W. Terry and G. G. Whelan, Plasma Phys. Controlled Fusion 56, 094003 (2014)] is extended to include electron temperature profile dynamics. It is shown that QSH dynamics is linked to the electron temperature profile because the suppression of mode coupling between tearing modes proposed to underlie QSH also suppresses magnetic-fluctuation-induced thermal transport. Above the threshold of dominant-mode shear that marks the transition to QSH, the model produces temperature-gradient steepening in the strong shear region. Oscillations of the dominant and secondary mode amplitudes give rise to oscillations of the temperature gradient. The phasing and amplitude of temperature gradient oscillations relative to those of the dominant mode are in agreement with experiment. This provides further evidence that the model, while heuristic, captures key physical aspects of the QSH state.

Ab-initio study of high temperature lattice dynamics of BCC zirconium (β-Zr) and uranium (γ-U)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghosh, Partha S., E-mail: parthasarathi13@gmail.com; Arya, A., E-mail: parthasarathi13@gmail.com; Dey, G. K., E-mail: parthasarathi13@gmail.com

2014-04-24

Using self consistent ab-initio lattice dynamics calculations, we show that bcc structures of Zr and U phases become stable at high temperature by phonon-phonon interactions. The calculated temperature dependent phonon dispersion curve (PDC) of β-Zr match excellently with experimental PDC. But the calculated PDC for γ-U shows negative phonon frequencies even at solid to liquid transition temperature. We show that this discrepancy is due to an overestimation of instability depth of bcc U phase which is removed by incorporation of spin-orbit coupling in the electronic structure calculations.

Evolution of the phonon density of states of LaCoO3 over the spin state transition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Golosova, N. O.; Kozlenko, D. P.; Kolesnikov, Alexander I

2011-01-01

The phonon spectra of LaCoO3 were studied by inelastic neutron scattering in the temperature range of 4 120 K. The DFT calculations of the lattice dynamics have been made for interpretation of the experimental data. The observed and calculated phonon frequencies were found to be in a reasonable agreement. The evolution of the phonon density of states over the spin state transition was analyzed. In the low-temperature range (T < 50 K), an increase in the energy of resolved breathing, stretching, and bending phonon modes was found, followed by their softening and broadening at higher temperatures due to the spinmore » state transition and relevant orbital-phonon coupling.« less

Brillouin-scattering study of liquid-glass transitions in ternary mixtures of water, trehalose, and an ionic liquid

NASA Astrophysics Data System (ADS)

Takayama, Haruki; Shibata, Tomohiko; Ishii, Takahiro; Kojima, Seiji

2013-04-01

Ternary mixtures of water, sugar, and ionic liquid have been studied as new candidates for bioprotectants. To clarify the elastic properties and relaxation dynamics of the supercooled liquid and glassy states at low temperatures, the liquid-glass transitions were investigated by using a micro-Brillouin-scattering technique. The refractive index was measured accurately as a function of content and temperature to determine the sound velocity and the attenuation from Brillouin frequency shift and peak width. The relaxation times of structural relaxations related to liquidglass transitions were determined as functions of temperature. The Meyer-Neldel rule was found to hold for the activation energy and the prefactor of the Arrhenius law for the relaxation time.

Generalization of soft phonon modes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rudin, Sven P.

Soft phonon modes describe a collective movement of atoms that transform a higher-symmetry crystal structure into a lower-symmetry crystal structure. Such structural transformations occur at finite temperatures, where the phonons (i.e., the low-temperature vibrational modes) and the static perfect crystal structures provide an incomplete picture of the dynamics. In this paper, principal vibrational modes (PVMs) are introduced as descriptors of the dynamics of a material system withmore » $N$ atoms. The PVMs represent the independent collective movements of the atoms at a given temperature. Molecular dynamics (MD) simulations, here in the form of quantum MD using density functional theory calculations, provide both the data describing the atomic motion and the data used to construct the PVMs. The leading mode, $${\\mathrm{PVM}}_{0}$$, represents the $3N$-dimensional direction in which the system moves with greatest amplitude. For structural phase transitions, $${\\mathrm{PVM}}_{0}$$ serves as a generalization of soft phonon modes. At low temperatures, $${\\mathrm{PVM}}_{0}$$ reproduces the soft phonon mode in systems where one phonon dominates the phase transformation. In general, multiple phonon modes combine to describe a transformation, in which case $${\\mathrm{PVM}}_{0}$$ culls these phonon modes. Moreover, while soft phonon modes arise in the higher-symmetry crystal structure, $${\\mathrm{PVM}}_{0}$$ can be equally well calculated on either side of the structural phase transition. Finally, two applications demonstrate these properties: first, transitions into and out of bcc titanium, and, second, the two crystal structures proposed for the $${\\beta}$$ phase of uranium, the higher-symmetry structure of which stabilizes with temperature.« less

Generalization of soft phonon modes

DOE PAGES

Rudin, Sven P.

2018-04-27

Soft phonon modes describe a collective movement of atoms that transform a higher-symmetry crystal structure into a lower-symmetry crystal structure. Such structural transformations occur at finite temperatures, where the phonons (i.e., the low-temperature vibrational modes) and the static perfect crystal structures provide an incomplete picture of the dynamics. In this paper, principal vibrational modes (PVMs) are introduced as descriptors of the dynamics of a material system withmore » $N$ atoms. The PVMs represent the independent collective movements of the atoms at a given temperature. Molecular dynamics (MD) simulations, here in the form of quantum MD using density functional theory calculations, provide both the data describing the atomic motion and the data used to construct the PVMs. The leading mode, $${\\mathrm{PVM}}_{0}$$, represents the $3N$-dimensional direction in which the system moves with greatest amplitude. For structural phase transitions, $${\\mathrm{PVM}}_{0}$$ serves as a generalization of soft phonon modes. At low temperatures, $${\\mathrm{PVM}}_{0}$$ reproduces the soft phonon mode in systems where one phonon dominates the phase transformation. In general, multiple phonon modes combine to describe a transformation, in which case $${\\mathrm{PVM}}_{0}$$ culls these phonon modes. Moreover, while soft phonon modes arise in the higher-symmetry crystal structure, $${\\mathrm{PVM}}_{0}$$ can be equally well calculated on either side of the structural phase transition. Finally, two applications demonstrate these properties: first, transitions into and out of bcc titanium, and, second, the two crystal structures proposed for the $${\\beta}$$ phase of uranium, the higher-symmetry structure of which stabilizes with temperature.« less

Technological parameters of welding of branch saddles to polyethylene pipes at low temperatures

NASA Astrophysics Data System (ADS)

Starostin, N. P.; Vasilieva, M. A.

2017-12-01

The present paper outlines a procedure for determination of dynamics of the temperature field during the welding of the branch saddle to the polyethylene gas pipeline at ambient temperatures below the normative. The analysis is accomplished by the finite element method with the heat of the phase transition taken into account. Methods of the visualization of data sets reveal the possibility of controlling the thermal process by preheating and thermal insulation during welding of the branch saddle to the pipe at low temperatures and the possibility of obtaining the dynamics of the temperature field at which a high-quality welded joint is formed.

Interface mobility and the liquid-glass transition in a one-component system described by an embedded atom method potential

NASA Astrophysics Data System (ADS)

Mendelev, M. I.; Schmalian, J.; Wang, C. Z.; Morris, J. R.; Ho, K. M.

2006-09-01

We present molecular dynamics (MD) studies of the liquid structure, thermodynamics, and dynamics in a one-component system described by the Ercolessi-Adams embedded atom method potential for Al. We find two distinct noncrystalline phases in this system. One of them is a liquid phase and the second phase has similar structure but different equation of state. Moreover, this phase has qualitatively different dynamics than that in the liquid phase. The transitions between these two noncrystalline phases can be seen during MD simulation. The hysteresis in this transition suggests that this is a first-order transition. This conclusion is strongly supported by simulations of the two phases that demonstrate that these phases may coexist with a well-defined interface. We find the coexistent temperature and the interface mobility. Finally, we discuss how these results can be explained using modern models of vitrification.

Fundamental differences between glassy dynamics in two and three dimensions

PubMed Central

Flenner, Elijah; Szamel, Grzegorz

2015-01-01

The two-dimensional freezing transition is very different from its three-dimensional counterpart. In contrast, the glass transition is usually assumed to have similar characteristics in two and three dimensions. Using computer simulations, here we show that glassy dynamics in supercooled two- and three-dimensional fluids are fundamentally different. Specifically, transient localization of particles on approaching the glass transition is absent in two dimensions, whereas it is very pronounced in three dimensions. Moreover, the temperature dependence of the relaxation time of orientational correlations is decoupled from that of the translational relaxation time in two dimensions but not in three dimensions. Last, the relationships between the characteristic size of dynamically heterogeneous regions and the relaxation time are very different in two and three dimensions. These results strongly suggest that the glass transition in two dimensions is different than in three dimensions. PMID:26067877

Shape dependent electronic structure and exciton dynamics in small In(Ga)As quantum dots

NASA Astrophysics Data System (ADS)

Gomis, J.; Martínez-Pastor, J.; Alén, B.; Granados, D.; García, J. M.; Roussignol, P.

2006-12-01

We present a study of the primary optical transitions and recombination dynamics in InGaAs self-assembled quantum nanostructures with different shape. Starting from the same quantum dot seeding layer, and depending on the overgrowth conditions, these new nanostructures can be tailored in shape and are characterized by heights lower than 2 nm and base lengths around 100 nm. The geometrical shape strongly influences the electronic and optical properties of these nanostructuctures. We measure for them ground state optical transitions in the range 1.25 1.35 eV and varying energy splitting between their excited states. The temperature dependence of the exciton recombination dynamics is reported focusing on the intermediate temperature regime (before thermal escape begins to be important). In this range, an important increase of the effective photoluminescence decay time is observed and attributed to the state filling and exciton thermalization between excited and ground states. A rate equation model is also developed reproducing quite well the observed exciton dynamics.

Density Functional Computations and Molecular Dynamics Simulations of the Triethylammonium Triflate Protic Ionic Liquid.

PubMed

Mora Cardozo, Juan F; Burankova, T; Embs, J P; Benedetto, A; Ballone, P

2017-12-21

Systematic molecular dynamics simulations based on an empirical force field have been carried out for samples of triethylammonium trifluoromethanesulfonate (triethylammonium triflate, [TEA][Tf]), covering a wide temperature range 200 K ≤ T ≤ 400 K and analyzing a broad set of properties, from self-diffusion and electrical conductivity to rotational relaxation and hydrogen-bond dynamics. The study is motivated by recent quasi-elastic neutron scattering and differential scanning calorimetry measurements on the same system, revealing two successive first order transitions at T ≈ 230 and 310 K (on heating), as well as an intriguing and partly unexplained variety of subdiffusive motions of the acidic proton. Simulations show a weakly discontinuous transition at T = 310 K and highlight an anomaly at T = 260 K in the rotational relaxation of ions that we identify with the simulation analogue of the experimental transition at T = 230 K. Thus, simulations help identifying the nature of the experimental transitions, confirming that the highest temperature one corresponds to melting, while the one taking place at lower T is a transition from the crystal, stable at T ≤ 260 K, to a plastic phase (260 ≤ T ≤ 310 K), in which molecules are able to rotate without diffusing. Rotations, in particular, account for the subdiffusive motion seen at intermediate T both in the experiments and in the simulation. The structure, distribution, and strength of hydrogen bonds are investigated by molecular dynamics and by density functional computations. Clustering of ions of the same sign and the effect of contamination by water at 1% wgt concentration are discussed as well.

On the molecular origin of the cooperative coil-to-globule transition of poly(N-isopropylacrylamide) in water† †Electronic supplementary information (ESI) available: Stereochemistry and initial conformation of PNIPAM 30-mer; pair distribution functions of PNIPAM methyl groups; average time of transitions of dihedral angles; distribution of methyl dihedral angles; temperature dependence of average number of hydration water molecules; correlation between hydrogen bonding of water molecules per repeating unit in the FHS and end to end distance and correlation between PNIPAM–water hydrogen bonding and end to end distance. Time evolution of PNIPAM with the first hydration shell: movie FHSpnipam.avi. See DOI: 10.1039/c8cp00537k

PubMed Central

Zaccarelli, E.

2018-01-01

By means of atomistic molecular dynamics simulations we investigate the behaviour of poly(N-isopropylacrylamide), PNIPAM, in water at temperatures below and above the lower critical solution temperature (LCST), including the undercooled regime. The transition between water soluble and insoluble states at the LCST is described as a cooperative process involving an intramolecular coil-to-globule transition preceding the aggregation of chains and the polymer precipitation. In this work we investigate the molecular origin of such cooperativity and the evolution of the hydration pattern in the undercooled polymer solution. The solution behaviour of an atactic 30-mer at high dilution is studied in the temperature interval from 243 to 323 K with a favourable comparison to available experimental data. In the water soluble states of PNIPAM we detect a correlation between polymer segmental dynamics and diffusion motion of bound water, occurring with the same activation energy. Simulation results show that below the coil-to-globule transition temperature PNIPAM is surrounded by a network of hydrogen bonded water molecules and that the cooperativity arises from the structuring of water clusters in proximity to hydrophobic groups. Differently, the perturbation of the hydrogen bond pattern involving water and amide groups occurs above the transition temperature. Altogether these findings reveal that even above the LCST PNIPAM remains largely hydrated and that the coil-to-globule transition is related with a significant rearrangement of the solvent in the proximity of the surface of the polymer. The comparison between the hydrogen bonding of water in the surrounding of PNIPAM isopropyl groups and in the bulk displays a decreased structuring of solvent at the hydrophobic polymer–water interface across the transition temperature, as expected because of the topological extension along the chain of such interface. No evidence of an upper critical solution temperature behaviour, postulated in theoretical and thermodynamics studies of PNIPAM aqueous solution, is observed in the low temperature domain. PMID:29619464

Molecular Origins of Thermal Transitions in Polyelectrolyte Assemblies

NASA Astrophysics Data System (ADS)

Yildirim, Erol; Zhang, Yanpu; Antila, Hanne S.; Lutkenhaus, Jodie L.; Sammalkorpi, Maria; Aalto Team; Texas A&M Team

2015-03-01

Polyelectrolyte (PE) multilayers and complexes formed from oppositely charged polymers can exhibit extraordinary superhydrophobicity, mechanical strength and responsiveness resulting in applications ranging functional membranes, optics, sensors and drug delivery. Depending on the assembly conditions, PE assemblies may undergo a thermal transition from glassy to soft behavior under heating. Our earlier work using thermal analysis measurements shows a distinct thermal transition for PE layer-by-layer (LbL) systems assembled with added salt but no analogous transition in films assembled without added salt or dry systems. These findings raise interesting questions on the nature of the thermal transition; here, we explore its molecular origins through characterization of the PE aggregates by temperature-controlled all-atom molecular dynamics simulations. We show via molecular simulations the thermal transition results from the existence of an LCST (lower critical solution temperature) in the PE systems: the diffusion behavior, hydrogen bond formation, and bridging capacity of water molecules plasticizing the complex changes at the transition temperature. We quantify the behavior, map its chemistry specificity through comparison of strongly and weakly charged PE complexes, and connect the findings to our interrelated QCM-D experiments.

Condensation of helium in aerogel and athermal dynamics of the random-field Ising model.

PubMed

Aubry, Geoffroy J; Bonnet, Fabien; Melich, Mathieu; Guyon, Laurent; Spathis, Panayotis; Despetis, Florence; Wolf, Pierre-Etienne

2014-08-22

High resolution measurements reveal that condensation isotherms of (4)He in high porosity silica aerogel become discontinuous below a critical temperature. We show that this behavior does not correspond to an equilibrium phase transition modified by the disorder induced by the aerogel structure, but to the disorder-driven critical point predicted for the athermal out-of-equilibrium dynamics of the random-field Ising model. Our results evidence the key role of nonequilibrium effects in the phase transitions of disordered systems.

In situ imaging of the dynamics of photo-induced structural phase transition at high pressures by picosecond acoustic interferometry

NASA Astrophysics Data System (ADS)

Kuriakose, Maju; Chigarev, Nikolay; Raetz, Samuel; Bulou, Alain; Tournat, Vincent; Zerr, Andreas; Gusev, Vitalyi E.

2017-05-01

Picosecond acoustic interferometry is used to monitor in time the motion of the phase transition boundary between two water ice phases, VII and VI, coexisting at a pressure of 2.15 GPa when compressed in a diamond anvil cell at room temperature. By analyzing the time-domain Brillouin scattering signals accumulated for a single incidence direction of probe laser pulses, it is possible to access ratios of sound velocity values and of the refractive indices of the involved phases, and to distinguish between the structural phase transition and a recrystallization process. Two-dimensional spatial imaging of the phase transition dynamics indicates that it is initiated by the pump and probe laser pulses, preferentially at the diamond/ice interface. This method should find applications in three-dimensional monitoring with nanometer spatial resolution of the temporal dynamics of low-contrast material inhomogeneities caused by phase transitions or chemical reactions in optically transparent media.

Using 20-million-year-old amber to test the super-Arrhenius behaviour of glass-forming systems.

PubMed

Zhao, Jing; Simon, Sindee L; McKenna, Gregory B

2013-01-01

Fossil amber offers the opportunity to investigate the dynamics of glass-forming materials far below the nominal glass transition temperature. This is important in the context of classical theory, as well as some new theories that challenge the idea of an 'ideal' glass transition. Here we report results from calorimetric and stress relaxation experiments using a 20-million-year-old Dominican amber. By performing the stress relaxation experiments in a step-wise fashion, we measured the relaxation time at each temperature and, above the fictive temperature of this 20-million-year-old glass, this is an upper bound to the equilibrium relaxation time. The results deviate dramatically from the expectation of classical theory and are consistent with some modern ideas, in which the diverging timescale signature of complex fluids disappears below the glass transition temperature.

Structural phase transition in d-benzil characterised by capacitance measurements and neutron powder diffraction

NASA Astrophysics Data System (ADS)

Goossens, D. J.; Wu, Xiaodong; Prior, M.

2005-12-01

The ferroelectric phase transition in deuterated benzil, C 14H 10O 2, has been studied using capacitance measurements and neutron powder diffraction. Hydrogenous benzil shows a phase transition at 83.5 K from a high temperature P3 121 phase to a cell-doubled P2 1 phase. The phase transition in d-benzil occurs at 88.1 K, a small isotope effect. Neutron powder diffraction was consistent with a low temperature phase of space group P2 1. Upon deuteration the transition remained first-order and the dynamics of the phenyl ring dominated the behaviour. The isotope effect can be attributed to the difference in mass and moment of inertia between C 6H 5 and C 6D 5.

An infrared spectroscopic study of the structural phase transition in the perovskite-type layer compound [ n-C 16H 33NH 3] 2CoCl 4

NASA Astrophysics Data System (ADS)

Ning, Guo; Guangfu, Zeng; Shiquan, Xi

1992-12-01

The solid-solid phase transitions in the perovskite-type layer compound [ n-C 16H 33NH 3] 2CoCl 4 have been studied by infrared spectroscopy. A new phase transition at 340 K was found by comparison with differential scanning calorimetry results. A temperature dependence study of the infrared spectra provides evidence of the occurrence of structural phase transitions related to the dynamics of the alkylammonium ions and hydrogen bonds. The main transition at 374 K corresponds to the conformational order-disorder change in the chain, which probably couples with reorientational motions of the NH 3 polar heads. GTG or GTG' defects appear in the high temperature disordered phase.

The effect of cross-linking on the molecular dynamics of the segmental and β Johari-Goldstein processes in polyvinylpyrrolidone-based copolymers.

PubMed

Redondo-Foj, Belén; Sanchis, María Jesús; Ortiz-Serna, Pilar; Carsí, Marta; García, José Miguel; García, Félix Clemente

2015-09-28

The effect of the cross-link density on the molecular dynamics of copolymers composed of vinylpyrrolidone (VP) and butyl acrylate (BA) was studied using differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS). A single glass transition was detected by DSC measurements. The dielectric spectra exhibit conductive processes and three dipolar relaxations labeled as α, β and γ in the decreasing order of temperatures. The cross-linker content affects both α and β processes, but the fastest γ process is relatively unaffected. An increase of cross-linking produces a typical effect on the α process dynamics: (i) the glass transition temperature is increased, (ii) the dispersion is broadened, (iii) its strength is decreased and (iv) the relaxation times are increased. However, the β process, which possesses typical features of a pure Johari-Goldstein relaxation, unexpectedly loses the intermolecular character for the highest cross-linker content.

Unfolding and melting of DNA (RNA) hairpins: the concept of structure-specific 2D dynamic landscapes.

PubMed

Lin, Milo M; Meinhold, Lars; Shorokhov, Dmitry; Zewail, Ahmed H

2008-08-07

A 2D free-energy landscape model is presented to describe the (un)folding transition of DNA/RNA hairpins, together with molecular dynamics simulations and experimental findings. The dependence of the (un)folding transition on the stem sequence and the loop length is shown in the enthalpic and entropic contributions to the free energy. Intermediate structures are well defined by the two coordinates of the landscape during (un)zipping. Both the free-energy landscape model and the extensive molecular dynamics simulations totaling over 10 mus predict the existence of temperature-dependent kinetic intermediate states during hairpin (un)zipping and provide the theoretical description of recent ultrafast temperature-jump studies which indicate that hairpin (un)zipping is, in general, not a two-state process. The model allows for lucid prediction of the collapsed state(s) in simple 2D space and we term it the kinetic intermediate structure (KIS) model.

On-the-fly transition search and applications to temperature-accelerated dynamics

NASA Astrophysics Data System (ADS)

Shim, Yunsic; Amar, Jacques

2015-03-01

Temperature-accelerated dynamics (TAD) is a powerful method to study non-equilibrium processes and has been providing surprising insights for a variety of systems. While serial TAD simulations have been limited by the roughly N3 increase in the computational cost as a function of the number of atoms N in the system, recently we have shown that by carrying out parallel TAD simulations which combine spatial decomposition with our semi-rigorous synchronous sublattice algorithm, significantly improved scaling is possible. However, in this approach the size of activated events is limited by the processor size while the dynamics is not exact. Here we discuss progress in improving the scaling of serial TAD by combining the use of on-the-fly transition searching with our previously developed localized saddle-point method. We demonstrate improved performance for the cases of Ag/Ag(100) annealing and Cu/Cu(100) growth. Supported by NSF DMR-1410840.

Properties of Ferroelectric Perovskite Structures under Non-equilibrium Conditions

NASA Astrophysics Data System (ADS)

Zhang, Qingteng

Ferroelectric materials have received lots of attention thanks to their intriguing properties such as the piezoelectric and pyroelectric effects, as well as the large dielectric constants and the spontaneous polarization which can potentially be used for information storage. In particular, perovskite crystal has a very simple unit cell structure yet a very rich phase transition diagram, which makes it one of the most intensively studied ferroelectric materials. In this dissertation, we use effective Hamiltonian, a first-principles-based computational technique to study the finite-temperature properties of ferroelectric perovskites. We studied temperature-graded (BaxSr 1-x)TiO3 (BST) bulk alloys as well as the dynamics of nanodomain walls (nanowalls) in Pb(Zr xTi1-x)O 3 (PZT) ultra-thin films under the driving force of an AC field. Our computations suggest that, for the temperature-graded BST, the polarization responds to the temperature gradient (TG), with the "up" and "down" offset observed in polarization components along the direction of TG, in agreement with the findings from experiments. For the nanowalls in PZT, the dynamics can be described by the damped-harmonic-oscillator model, and we observed a size-driven transition from resonance to relaxational dynamics at a critical thickness of 7.2 nm. The transition originates from the change in the effective mass of a nanowall as a film thickness increases. Some of the findings may find potential applications in various devices, such as thermal sensors, energy converters, or novel memory units.

Characterization of the glass transition of water predicted by molecular dynamics simulations using nonpolarizable intermolecular potentials.

PubMed

Kreck, Cara A; Mancera, Ricardo L

2014-02-20

Molecular dynamics simulations allow detailed study of the experimentally inaccessible liquid state of supercooled water below its homogeneous nucleation temperature and the characterization of the glass transition. Simple, nonpolarizable intermolecular potentials are commonly used in classical molecular dynamics simulations of water and aqueous systems due to their lower computational cost and their ability to reproduce a wide range of properties. Because the quality of these predictions varies between the potentials, the predicted glass transition of water is likely to be influenced by the choice of potential. We have thus conducted an extensive comparative investigation of various three-, four-, five-, and six-point water potentials in both the NPT and NVT ensembles. The T(g) predicted from NPT simulations is strongly correlated with the temperature of minimum density, whereas the maximum in the heat capacity plot corresponds to the minimum in the thermal expansion coefficient. In the NVT ensemble, these points are instead related to the maximum in the internal pressure and the minimum of its derivative, respectively. A detailed analysis of the hydrogen-bonding properties at the glass transition reveals that the extent of hydrogen-bonds lost upon the melting of the glassy state is related to the height of the heat capacity peak and varies between water potentials.

Car-Parrinello molecular dynamics study of the melting behaviors of n-atom (n = 6, 10) graphene quantum dots

NASA Astrophysics Data System (ADS)

Shekaari, Ashkan; Abolhassani, Mohammad Reza

2017-06-01

First-principles molecular dynamics has been applied to inquire into the melting behaviors of n-atom (n = 6, 10) graphene quantum dots (GQD6 and zigzag GQD10) within the temperature range of T = 0-500 K. The temperature dependence of the geometry of each quantum dot is thoroughly evaluated via calculating the related shape deformation parameters and the eigenvalues of the quadrupole tensors. Examining the variations of some phase-transition indicators such as root-mean-square bond length fluctuations and mean square displacements broadly proposes the value of Tm = 70 K for the melting point of GQD6 while a continuous, two-stage phase transition has been concluded for zigzag GQD10.

Quantum effects in the dynamics of deeply supercooled water

DOE PAGES

Agapov, Alexander L.; Kolesnikov, Alexander I.; Novikov, Vladimir N.; ...

2015-02-26

In spite of its simple chemical structure, water remains one of the most puzzling liquids with many anomalies at low temperatures. Combining neutron scattering and dielectric relaxation spectroscopy, we show that quantum fluctuations are not negligible in deeply supercooled water. Our dielectric measurements reveal the anomalously weak temperature dependence of structural relaxation in vapor-deposited water close to the glass transition temperature T g~136K. We demonstrate that this anomalous behavior can be explained well by quantum effects. In conclusion, these results have significant implications for our understanding of water dynamics.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glynos, Emmanouil; Johnson, Kyle J.; Frieberg, Bradley

The surface relaxation dynamics of supported star-shaped polymer thin films are shown to be slower than the bulk, persisting up to temperatures at least 50 K above the bulk glass transition temperature Tgbulk. This behavior, exhibited by star-shaped polystyrenes with functionality f=8 arms and molecular weights per arm Marm

Two-dimensional electronic spectroscopy signatures of the glass transition

DOE PAGES

Lewis, K. L. .. M.; Myers, J. A.; Fuller, F.; ...

2010-01-01

Two-dimensional electronic spectroscopy is a sensitive probe of solvation dynamics. Using a pump–probe geometry with a pulse shaper [ Optics Express 15 (2007), 16681-16689; Optics Express 16 (2008), 17420-17428], we present temperature dependent 2D spectra of laser dyes dissolved in glass-forming solvents. At low waiting times, the system has not yet relaxed, resulting in a spectrum that is elongated along the diagonal. At longer times, the system loses its memory of the initial excitation frequency, and the 2D spectrum rounds out. As the temperature is lowered, the time scale of this relaxation grows, and the elongation persists for longer waitingmore » times. This can be measured in the ratio of the diagonal width to the anti-diagonal width; the behavior of this ratio is representative of the frequency–frequency correlation function [ Optics Letters 31 (2006), 3354–3356]. Near the glass transition temperature, the relaxation behavior changes. Understanding this change is important for interpreting temperature-dependent dynamics of biological systems.« less

Localized to itinerant transition of f electrons in ordered Ce films on W(110)

NASA Astrophysics Data System (ADS)

Chen, Q. Y.; Feng, W.; Xie, D. H.; Lai, X. C.; Zhu, X. G.; Huang, L.

2018-04-01

A key issue to understand the driving force and underlying physics in the isostructural γ -α transition in Cerium is the character of the 4 f states, whether it is localized or itinerant. Here the surface topography and electronic structure of the well-ordered Ce metal films on a W(110) substrate were investigated by using scanning tunneling microscopy, angle-resolved photoemission spectroscopy and density functional theory, and single-site dynamical mean-field theory calculations. Three nearly flat f bands can be observed, and a weakly dispersive quasiparticle band near the Fermi level has been directly observed at low temperature, indicating the hybridization between f electrons and conduction electrons in the low-temperature α phase. The hybridization strength becomes weaker upon increasing temperature, and the f electrons become almost fully localized at 300 K in the high-temperature γ phase. The observed localized-to-itinerant transition of the f electrons with decreasing temperature gives direct experimental proof for the changes of the 4 f character in the isostructural γ -α phase transition. Our results suggest that the character of the f electrons plays a crucial role during the γ -α phase transition.

Prediction of the glass transition in aqueous solutions of simple amides by molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Kreck, Cara A.; Mandumpal, Jestin B.; Mancera, Ricardo L.

2011-01-01

Some simple amides in aqueous solution are used in the cryopreservation of biological tissues as they are believed to promote the vitrification of water, inhibiting its crystallisation and the ensuing damage from ice formation. Molecular dynamics annealing simulations reveal a broadening in the glass transition of aqueous acetamide and N-methylacetamide solutions, suggesting a thermodynamic stabilisation of the glassy state, which may be responsible for their increased tendency of vitrification and their cryoprotective ability. By contrast, aqueous formamide solutions do not exhibit broadening of the glass transition; instead, it is shifted to lower temperatures, which explains their lack of vitrification properties.

Low Dose X-Ray Speckle Visibility Spectroscopy Reveals Nanoscale Dynamics in Radiation Sensitive Ionic Liquids

NASA Astrophysics Data System (ADS)

Verwohlt, Jan; Reiser, Mario; Randolph, Lisa; Matic, Aleksandar; Medina, Luis Aguilera; Madsen, Anders; Sprung, Michael; Zozulya, Alexey; Gutt, Christian

2018-04-01

X-ray radiation damage provides a serious bottleneck for investigating microsecond to second dynamics on nanometer length scales employing x-ray photon correlation spectroscopy. This limitation hinders the investigation of real time dynamics in most soft matter and biological materials which can tolerate only x-ray doses of kGy and below. Here, we show that this bottleneck can be overcome by low dose x-ray speckle visibility spectroscopy. Employing x-ray doses of 22-438 kGy and analyzing the sparse speckle pattern of count rates as low as 6.7 ×10-3 per pixel, we follow the slow nanoscale dynamics of an ionic liquid (IL) at the glass transition. At the prepeak of nanoscale order in the IL, we observe complex dynamics upon approaching the glass transition temperature TG with a freezing in of the alpha relaxation and a multitude of millisecond local relaxations existing well below TG . We identify this fast relaxation as being responsible for the increasing development of nanoscale order observed in ILs at temperatures below TG .

Emergent phases and critical behavior in a non-Markovian open quantum system

NASA Astrophysics Data System (ADS)

Cheung, H. F. H.; Patil, Y. S.; Vengalattore, M.

2018-05-01

Open quantum systems exhibit a range of novel out-of-equilibrium behavior due to the interplay between coherent quantum dynamics and dissipation. Of particular interest in these systems are driven, dissipative transitions, the emergence of dynamical phases with novel broken symmetries, and critical behavior that lies beyond the conventional paradigm of Landau-Ginzburg phenomenology. Here, we consider a parametrically driven two-mode system in the presence of non-Markovian system-reservoir interactions. We show that the non-Markovian dynamics modifies the phase diagram of this system, resulting in the emergence of a broken symmetry phase in a universality class that has no counterpart in the corresponding Markovian system. This emergent phase is accompanied by enhanced two-mode entanglement that remains robust at finite temperatures. Such reservoir-engineered dynamical phases can potentially shed light on universal aspects of dynamical phase transitions in a wide range of nonequilibrium systems, and aid in the development of techniques for the robust generation of entanglement and quantum correlations at finite temperatures with potential applications to quantum control, state preparation, and metrology.

Collective Dynamics and Strong Pinning near the Onset of Charge Order in La1.48Nd0.4Sr0.12CuO4

NASA Astrophysics Data System (ADS)

Baity, P. G.; Sasagawa, T.; Popović, Dragana

2018-04-01

The dynamics of charge-ordered states is one of the key issues in underdoped cuprate high-temperature superconductors, but static short-range charge-order (CO) domains have been detected in almost all cuprates. We probe the dynamics across the CO (and structural) transition in La1.48Nd0.4Sr0.12CuO4 by measuring nonequilibrium charge transport, or resistance R as the system responds to a change in temperature and to an applied magnetic field. We find evidence for metastable states, collective behavior, and criticality. The collective dynamics in the critical regime indicates strong pinning by disorder. Surprisingly, nonequilibrium effects, such as avalanches in R , are revealed only when the critical region is approached from the charge-ordered phase. Our results on La1.48Nd0.4Sr0.12CuO4 provide the long-sought evidence for the fluctuating order across the CO transition, and also set important constraints on theories of dynamic stripes.

Irradiation defect dispersions and effective dislocation mobility in strained ferritic grains: A statistical analysis based on 3D dislocation dynamics simulations

NASA Astrophysics Data System (ADS)

Li, Y.; Robertson, C.

2018-06-01

The influence of irradiation defect dispersions on plastic strain spreading is investigated by means of three-dimensional dislocation dynamics (DD) simulations, accounting for thermally activated slip and cross-slip mechanisms in Fe-2.5%Cr grains. The defect-induced evolutions of the effective screw dislocation mobility are evaluated by means of statistical comparisons, for various defect number density and defect size cases. Each comparison is systematically associated with a quantitative Defect-Induced Apparent Straining Temperature shift (or «ΔDIAT»), calculated without any adjustable parameters. In the investigated cases, the ΔDIAT level associated with a given defect dispersion closely replicates the measured ductile to brittle transition temperature shift (ΔDBTT) due to the same, actual defect dispersion. The results are further analyzed in terms of dislocation-based plasticity mechanisms and their possible relations with the dose-dependent changes of the ductile to brittle transition temperature.

Investigating the Pressure-Induced Amorphization of Zeolitic Imidazolate Framework ZIF-8: Mechanical Instability Due to Shear Mode Softening.

PubMed

Ortiz, Aurélie U; Boutin, Anne; Fuchs, Alain H; Coudert, François-Xavier

2013-06-06

We provide the first molecular dynamics study of the mechanical instability that is the cause of pressure-induced amorphization of zeolitic imidazolate framework ZIF-8. By measuring the elastic constants of ZIF-8 up to the amorphization pressure, we show that the crystal-to-amorphous transition is triggered by the mechanical instability of ZIF-8 under compression, due to shear mode softening of the material. No similar softening was observed under temperature increase, explaining the absence of temperature-induced amorphization in ZIF-8. We also demonstrate the large impact of the presence of adsorbate in the pores on the mechanical stability and compressibility of the framework, increasing its shear stability. This first molecular dynamics study of ZIF mechanical properties under variations of pressure, temperature, and pore filling opens the way to a more comprehensive understanding of their mechanical stability, structural transitions, and amorphization.

Evidence for reentrant spin glass behavior in transition metal substituted Co-Ga alloys near critical concentration

NASA Astrophysics Data System (ADS)

Yasin, Sk. Mohammad; Srinivas, V.; Kasiviswanathan, S.; Vagadia, Megha; Nigam, A. K.

2018-04-01

In the present study magnetic and electrical transport properties of transition metal substituted Co-Ga alloys (near critical cobalt concentration) have been investigated. Analysis of temperature and field dependence of dc magnetization and ac susceptibility (ACS) data suggests an evidence of reentrant spin glass (RSG) phase in Co55.5TM3Ga41.5 (TM = Co, Cr, Fe, Cu). The magnetic transition temperatures (TC and Tf) are found to depend on the nature of TM element substitution with the exchange coupling strength Co-Fe > Co-Co > Co-Cu > Co-Cr. From magnetization dynamics precise transition temperatures for the glassy phases are estimated. It is found that characteristic relaxation times are higher than that of spin glasses with minimal spin-cluster formation. The RSG behavior has been further supported by the temperature dependence of magnetotransport studies. From the magnetic field and substitution effects it has been established that the magnetic and electrical transport properties are correlated in this system.

Glass Transition and Molecular Mobility in Styrene-Butadiene Rubber Modified Asphalt.

PubMed

Khabaz, Fardin; Khare, Rajesh

2015-11-05

Asphalt, a soft matter consisting of more than a thousand chemical species, is of vital importance for the transportation infrastructure, yet it poses significant challenges for microscopic theory and modeling approaches due to its multicomponent nature. Polymeric additives can potentially enhance the thermo-mechanical properties of asphalt, thus helping reduce the road repair costs; rational design of such systems requires knowledge of the molecular structure and dynamics of these systems. We have used molecular dynamics (MD) simulations to investigate the volumetric, structural, and dynamic properties of the neat asphalt as well as styrene-butadiene rubber (SBR) modified asphalt systems. The volume-temperature behavior of the asphalt systems exhibited a glass transition phenomenon, akin to that observed in experiments. The glass transition temperature, room temperature density, and coefficient of volume thermal expansion of the neat asphalt systems so evaluated were in agreement with experimental data when the effect of the high cooling rate used in simulations was accounted for. While the volumetric properties of SBR modified asphalt were found to be insensitive to the presence of the SBR additive, the addition of SBR led to an increase in the aggregation of asphaltene molecules. Furthermore, addition of SBR caused a reduction in the mobility of the constituent molecules of asphalt, with the reduction being more significant for the larger constituent molecules. Similar to other glass forming liquids, the reciprocal of the diffusion coefficient of the selected molecules was observed to follow the Vogel-Fulcher-Tammann (VFT) behavior as a function of temperature. These results suggest the potential for using polymeric additives for enhancing the dynamic mechanical properties of asphalt without affecting its volumetric properties.

Kinetics from Replica Exchange Molecular Dynamics Simulations.

PubMed

Stelzl, Lukas S; Hummer, Gerhard

2017-08-08

Transitions between metastable states govern many fundamental processes in physics, chemistry and biology, from nucleation events in phase transitions to the folding of proteins. The free energy surfaces underlying these processes can be obtained from simulations using enhanced sampling methods. However, their altered dynamics makes kinetic and mechanistic information difficult or impossible to extract. Here, we show that, with replica exchange molecular dynamics (REMD), one can not only sample equilibrium properties but also extract kinetic information. For systems that strictly obey first-order kinetics, the procedure to extract rates is rigorous. For actual molecular systems whose long-time dynamics are captured by kinetic rate models, accurate rate coefficients can be determined from the statistics of the transitions between the metastable states at each replica temperature. We demonstrate the practical applicability of the procedure by constructing master equation (Markov state) models of peptide and RNA folding from REMD simulations.

Dynamics of antiferroelectric phase transition in PbZrO 3

DOE PAGES

Fthenakis, Z. G.; Ponomareva, Inna

2017-11-27

The dynamics of the phase transition in antiferroelectric PbZrO 3 which is a subject of a decades long debate, is examined using first-principles-based simulations. This is achieved through development of a computational approach that allows calculations of generalized complex susceptibilities at an arbitrary point of the Brillouin zone. Application of this approach to the case of PbZrO 3 predicts the temperature evolution of many of its lattice modes, some of which remain elusive or even ``invisible'' in experiments. Here, the computational data suggest that two lattice modes are primarily responsible for the antiferroelectric phase transition in this material: the onemore » associated with oxygen octahedra tilts dynamics and the other due to lead ions antipolar vibrations.« less

Electrocaloric effect in BaTiO3 at all three ferroelectric transitions: Anisotropy and inverse caloric effects

NASA Astrophysics Data System (ADS)

Marathe, Madhura; Renggli, Damian; Sanlialp, Mehmet; Karabasov, Maksim O.; Shvartsman, Vladimir V.; Lupascu, Doru C.; Grünebohm, Anna; Ederer, Claude

2017-07-01

We study the electrocaloric (EC) effect in bulk BaTiO3 (BTO) using molecular dynamics simulations of a first principles-based effective Hamiltonian, combined with direct measurements of the adiabatic EC temperature change in BTO single crystals. We examine in particular the dependence of the EC effect on the direction of the applied electric field at all three ferroelectric transitions, and we show that the EC response is strongly anisotropic. Most strikingly, an inverse caloric effect, i.e., a temperature increase under field removal, can be observed at both ferroelectric-ferroelectric transitions for certain orientations of the applied field. Using the generalized Clausius-Clapeyron equation, we show that the inverse effect occurs exactly for those cases where the field orientation favors the higher temperature/higher entropy phase. Our simulations show that temperature changes of around 1 K can, in principle, be obtained at the tetragonal-orthorhombic transition close to room temperature, even for small applied fields, provided that the applied field is strong enough to drive the system across the first-order transition line. Our direct EC measurements for BTO single crystals at the cubic-tetragonal and at the tetragonal-orthorhombic transitions are in good qualitative agreement with our theoretical predictions, and in particular confirm the occurrence of an inverse EC effect at the tetragonal-orthorhombic transition for electric fields applied along the [001] pseudocubic direction.

Nonlinear dielectric spectroscopy in a fragile plastic crystal

NASA Astrophysics Data System (ADS)

Michl, M.; Bauer, Th.; Lunkenheimer, P.; Loidl, A.

2016-03-01

In this work we provide a thorough examination of the nonlinear dielectric properties of a succinonitrile-glutaronitrile mixture, representing one of the rare examples of a plastic crystal with fragile glassy dynamics. The detected alteration of the complex dielectric permittivity under high fields can be explained considering the heterogeneous nature of glassy dynamics and a field-induced variation of entropy. While the first mechanism was also found in structural glass formers, the latter effect seems to be more pronounced in plastic crystals. Moreover, the third harmonic component of the dielectric susceptibility is reported, revealing a hump-like spectral shape as predicted, e.g., within a model considering cooperative molecular dynamics. If assuming the validity of this model, one can deduce the temperature dependence of the number of correlated molecules Ncorr from these data. In accord with the fragile nature of the glass transition in this plastic crystal, we obtain a relatively strong temperature dependence of Ncorr, in contrast to the much weaker temperature dependence in plastic-crystalline cyclo-octanol, whose glass transition is of strong nature.

Extensional Flow-Induced Dynamic Phase Transitions in Isotactic Polypropylene.

PubMed

Ju, Jianzhu; Wang, Zhen; Su, Fengmei; Ji, Youxin; Yang, Haoran; Chang, Jiarui; Ali, Sarmad; Li, Xiangyang; Li, Liangbin

2016-09-01

With a combination of fast extension rheometer and in situ synchrotron radiation ultra-fast small- and wide-angle X-ray scattering, flow-induced crystallization (FIC) of isotactic polypropylene (iPP) is studied at temperatures below and above the melting point of α crystals (Tmα). A flow phase diagram of iPP is constructed in strain rate-temperature space, composing of melt, non-crystalline shish, α and α&β coexistence regions, based on which the kinetic and dynamic competitions among these four phases are discussed. Above Tmα , imposing strong flow reverses thermodynamic stabilities of the disordered melt and the ordered phases, leading to the occurrence of FIC of β and α crystals as a dynamic phase transition. Either increasing temperature or stain rate favors the competiveness of the metastable β over the stable α crystals, which is attributed to kinetic rate rather than thermodynamic stability. The violent competitions among four phases near the boundary of crystal-melt may frustrate crystallization and result in the non-crystalline shish winning out. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Configurational entropy of polar glass formers and the effect of electric field on glass transition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matyushov, Dmitry V., E-mail: dmitrym@asu.edu

2016-07-21

A model of low-temperature polar liquids is constructed that accounts for the configurational heat capacity, entropy, and the effect of a strong electric field on the glass transition. The model is based on the Padé-truncated perturbation expansions of the liquid state theory. Depending on parameters, it accommodates an ideal glass transition of vanishing configurational entropy and its avoidance, with a square-root divergent enumeration function at the point of its termination. A composite density-temperature parameter ρ{sup γ}/T, often used to represent combined pressure and temperature data, follows from the model. The theory is in good agreement with the experimental data formore » excess (over the crystal state) thermodynamics of molecular glass formers. We suggest that the Kauzmann entropy crisis might be a signature of vanishing configurational entropy of a subset of degrees of freedom, multipolar rotations in our model. This scenario has observable consequences: (i) a dynamical crossover of the relaxation time and (ii) the fragility index defined by the ratio of the excess heat capacity and excess entropy at the glass transition. The Kauzmann temperature of vanishing configurational entropy and the corresponding glass transition temperature shift upward when the electric field is applied. The temperature shift scales quadratically with the field strength.« less

Field-Induced Transitions in Anisotropic Kondo Lattice — Application to CeT2Al10 —

NASA Astrophysics Data System (ADS)

Kikuchi, Taku; Hoshino, Shintaro; Shibata, Naokazu; Kuramoto, Yoshio

2017-09-01

The magnetic properties of an anisotropic Kondo lattice are investigated under a magnetic field using dynamical mean field theory and the continuous-time quantum Monte Carlo method. The magnetic phase diagram is determined from the temperature dependence of both uniform and staggered magnetizations in magnetic fields. We find a spin-flop transition inside the antiferromagnetic (AF) phase, whose transition field increases with increasing Kondo coupling while the AF transition temperature decreases. These results cannot be described by a simple spin Hamiltonian and are consistent with the experimental results of the field-induced transition observed in CeT2Al10 (T = Ru, Os). The anisotropic susceptibilities of CeT2Al10 are reproduced in the whole temperature range by incorporating the effects of the crystalline electric field (CEF) in the anisotropic Kondo lattice. We also propose a possible explanation for the difference in anisotropies between the magnetic susceptibility and AF moments observed in experiments.

Effective equilibrium picture in the x y model with exponentially correlated noise

NASA Astrophysics Data System (ADS)

Paoluzzi, Matteo; Marconi, Umberto Marini Bettolo; Maggi, Claudio

2018-02-01

We study the effect of exponentially correlated noise on the x y model in the limit of small correlation time, discussing the order-disorder transition in the mean field and the topological transition in two dimensions. We map the steady states of the nonequilibrium dynamics into an effective equilibrium theory. In the mean field, the critical temperature increases with the noise correlation time τ , indicating that memory effects promote ordering. This finding is confirmed by numerical simulations. The topological transition temperature in two dimensions remains untouched. However, finite-size effects induce a crossover in the vortices proliferation that is confirmed by numerical simulations.

A numerical study of transition control by periodic suction-blowing

NASA Technical Reports Server (NTRS)

Biringen, Sedat

1987-01-01

The applicability of active control of transition by periodic suction-blowing is investigated via direct numerical simulations of the Navier-Stokes equations. The time-evolution of finite-amplitude disturbances in plane channel flow is compared in detail with and without control. The analysis indicates that, for relatively small three dimensional amplitudes, a two dimensional control effectively reduces disturbance growth rates even for linearly unstable Reynolds numbers. After the flow goes through secondary instability, three dimensional control seems necessary to stabilize the flow. An investigation of the temperature field suggests that passive temperature contamination is operative to reflect the flow dynamics during transition.

Effective equilibrium picture in the xy model with exponentially correlated noise.

PubMed

Paoluzzi, Matteo; Marconi, Umberto Marini Bettolo; Maggi, Claudio

2018-02-01

We study the effect of exponentially correlated noise on the xy model in the limit of small correlation time, discussing the order-disorder transition in the mean field and the topological transition in two dimensions. We map the steady states of the nonequilibrium dynamics into an effective equilibrium theory. In the mean field, the critical temperature increases with the noise correlation time τ, indicating that memory effects promote ordering. This finding is confirmed by numerical simulations. The topological transition temperature in two dimensions remains untouched. However, finite-size effects induce a crossover in the vortices proliferation that is confirmed by numerical simulations.

Theoretical study of superionic phase transition in Li2S.

PubMed

Jand, Sara Panahian; Zhang, Qian; Kaghazchi, Payam

2017-07-19

We have studied temperature-induced superionic phase transition in Li 2 S, which is one of the most promising Li-S battery cathode material. Concentration of ionic carriers at low and high temperature was evaluated from thermodynamics of defects (using density functional theory) and detailed balance condition (using ab initio molecular dynamics (AIMD)), respectively. Diffusion coefficients were also obtained using AIMD simulations. Calculated ionic conductivity shows that superionic phase transition occurs at T = 900 K, which is in agreement with reported experimental values. The superionic behavior of Li 2 S is found to be due to thermodynamic reason (i.e. a large concentration of disordered defects).

Nature of the first-order liquid-liquid phase transition in supercooled silicon

NASA Astrophysics Data System (ADS)

Zhao, G.; Yu, Y. J.; Tan, X. M.

2015-08-01

The first-order liquid-liquid phase transition in supercooled Si is revisited by long-time first-principle molecular dynamics simulations. As the focus of the present paper, its nature is revealed by analyzing the inherent structures of low-density liquid (LDL) and high-density liquid (HDL). Our results show that it is a transition between a sp3-hybridization LDL and a white-tin-like HDL. This uncovers the origin of the semimetal-metal transition accompanying it and also proves that HDL is the metastable extension of high temperature equilibrium liquid into the supercooled regime. The pressure-temperature diagram of supercooled Si thus can be regarded in some respects as shifted reflection of its crystalline phase diagram.

Properties of planetary fluids at high pressure and temperature

NASA Technical Reports Server (NTRS)

Nellis, W. J.; Hamilton, D. C.; Holmes, N. C.; Radousky, H. B.; Ree, F. H.; Ross, M.; Young, D. A.; Nicol, M.

1987-01-01

In order to derive models of the interiors of Uranus, Neptune, Jupiter and Saturn, researchers studied equations of state and electrical conductivities of molecules at high dynamic pressures and temperatures. Results are given for shock temperature measurements of N2 and CH4. Temperature data allowed demonstration of shock induced cooling in the the transition region and the existence of crossing isotherms in P-V space.

On the nature of the Mott transition in multiorbital systems

NASA Astrophysics Data System (ADS)

Facio, Jorge I.; Vildosola, V.; García, D. J.; Cornaglia, Pablo S.

2017-02-01

We analyze the nature of a Mott metal-insulator transition in multiorbital systems using dynamical mean-field theory. The auxiliary multiorbital quantum impurity problem is solved using continuous-time quantum Monte Carlo and the rotationally invariant slave-boson (RISB) mean-field approximation. We focus our analysis on the Kanamori Hamiltonian and find that there are two markedly different regimes determined by the nature of the lowest-energy excitations of the atomic Hamiltonian. The RISB results at T →0 suggest the following rule of thumb for the order of the transition at zero temperature: a second-order transition is to be expected if the lowest-lying excitations of the atomic Hamiltonian are charge excitations, while the transition tends to be first order if the lowest-lying excitations are in the same charge sector as the atomic ground state. At finite temperatures, the transition is first order and its strength, as measured, e.g., by the jump in the quasiparticle weight at the transition, is stronger in the parameter regime where the RISB method predicts a first-order transition at zero temperature. Interestingly, these results seem to apply to a wide variety of models and parameter regimes.

Monitoring a Silent Phase Transition in CH 3NH 3PbI 3 Solar Cells via Operando X-ray Diffraction

DOE PAGES

Schelhas, Laura T.; Christians, Jeffrey A.; Berry, Joseph J.; ...

2016-10-13

The relatively modest temperature of the tetragonal-to-cubic phase transition in CH 3NH 3PbI 3 perovskite is likely to occur during real world operation of CH 3NH 3PbI 3 solar cells. In this work, we simultaneously monitor the structural phase transition of the active layer along with solar cell performance as a function of the device operating temperature. The tetragonal to cubic phase transition is observed in the working device to occur reversibly at temperatures between 60.5 and 65.4 degrees C. In these operando measurements, no discontinuity in the device performance is observed, indicating electronic behavior that is insensitive to themore » structural phase transition. Here, this decoupling of device performance from the change in long-range order across the phase transition suggests that the optoelectronic properties are primarily determined by the local structure in CH 3NH 3PbI 3. That is, while the average crystal structure as probed by X-ray diffraction shows a transition from tetragonal to cubic, the local structure generally remains well characterized by uncorrelated, dynamic octahedral rotations that order at elevated temperatures but are unchanged locally.« less

Monitoring a Silent Phase Transition in CH 3NH 3PbI 3 Solar Cells via Operando X-ray Diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schelhas, Laura T.; Christians, Jeffrey A.; Berry, Joseph J.

The relatively modest temperature of the tetragonal-to-cubic phase transition in CH 3NH 3PbI 3 perovskite is likely to occur during real world operation of CH 3NH 3PbI 3 solar cells. In this work, we simultaneously monitor the structural phase transition of the active layer along with solar cell performance as a function of the device operating temperature. The tetragonal to cubic phase transition is observed in the working device to occur reversibly at temperatures between 60.5 and 65.4 degrees C. In these operando measurements, no discontinuity in the device performance is observed, indicating electronic behavior that is insensitive to themore » structural phase transition. Here, this decoupling of device performance from the change in long-range order across the phase transition suggests that the optoelectronic properties are primarily determined by the local structure in CH 3NH 3PbI 3. That is, while the average crystal structure as probed by X-ray diffraction shows a transition from tetragonal to cubic, the local structure generally remains well characterized by uncorrelated, dynamic octahedral rotations that order at elevated temperatures but are unchanged locally.« less

Temperature-dependent dynamical transitions of different classes of amino acid residue in a globular protein.

PubMed

Miao, Yinglong; Yi, Zheng; Glass, Dennis C; Hong, Liang; Tyagi, Madhusudan; Baudry, Jerome; Jain, Nitin; Smith, Jeremy C

2012-12-05

The temperature dependences of the nanosecond dynamics of different chemical classes of amino acid residue have been analyzed by combining elastic incoherent neutron scattering experiments with molecular dynamics simulations on cytochrome P450cam. At T = 100-160 K, anharmonic motion in hydrophobic and aromatic residues is activated, whereas hydrophilic residue motions are suppressed because of hydrogen-bonding interactions. In contrast, at T = 180-220 K, water-activated jumps of hydrophilic side chains, which are strongly coupled to the relaxation rates of the hydrogen bonds they form with hydration water, become apparent. Thus, with increasing temperature, first the hydrophobic core awakens, followed by the hydrophilic surface.

Magnetic Properties and Phase Composition of Metamaterials Based on an Opal Matrix with 3 d-Transition Metal Particles

NASA Astrophysics Data System (ADS)

Rinkevich, A. B.; Korolev, A. V.; Samoilovich, M. I.; Perov, D. V.; Nemytova, O. V.

2018-02-01

The magnetic properties of metamaterials based on an opal matrix with transition-metal (iron, nickel, cobalt) particles have been studied. Magnetization curves and magnetic hysteresis loops have been measured and the dependences of real and imaginary parts of magnetization have been determined using the dynamic ac susceptibility measuring procedure. Structural studies of metamaterials have been performed. The saturation magnetization and coercive force of the studied metamaterials have been found to depend weakly on the temperature. The temperature dependence of magnetic susceptibility at a temperature above 30 K can be described adequately by Curie-Weiss law and, at lower temperature, deviates from the law.

Subducted Slab Dynamics: Toward Understanding the Causes of Slab Stagnation

NASA Astrophysics Data System (ADS)

King, S. D.; Frost, D. J.; Rubie, D. C.

2013-12-01

The evolution and dynamics of subducted slabs are controlled by a number of factors, including rheology and composition. The correlation of the transformations from olivine to wadslayite and ringwoodite to perovskite plus magnesiowüstite with the seismic velocity discontinuities at 410 and 660 km depth, along with the density changes have been extensively investigated in terms of their impact on slab dynamics. Owing to the relatively smaller changes in density extending over a broader depth range, the impact of the pyroxene-garnet system has received less attention. Recent experimental work has found that the majorite component in garnet--a product of the transition from pyroxene into garnet--is one of the slowest-diffusing components in Earth's mantle. At the relatively low temperatures of the slab, this slow diffusion inhibits the dissolution of pyroxene into garnet, so that the slab remains buoyant relative to the ambient mantle and stagnates. We present dynamic subduction calculations that illustrate the effect of the non-equilibrium pyroxene to garnet transition on slab dynamics. If the transition between equilibrium and non-equilibrium behavior is below 1000 K, we find no impact on slab dynamics. If the transition occurs at 1200 K, it is enough to cause the slab to thicken and stagnate in the transition zone for an extended period of time. Our analysis suggests that cold slabs should be more likely to stagnate in the transition zone and we will compare a global compilation of slab geometries with slab thermal structure to evaluate.

Calculated temperature dependence of elastic constants and phonon dispersion of hcp and bcc beryllium

NASA Astrophysics Data System (ADS)

Hahn, Steven; Arapan, Sergiu; Harmon, Bruce; Eriksson, Olle

2011-03-01

Conventional first principle methods for calculating lattice dynamics are unable to calculate high temperature thermophysical properties of materials containing modes that are entropically stabilized. In this presentation we use a relatively new approach called self-consistent ab initio lattice dynamics (SCAILD) to study the hcp to bcc transition (1530 K) in beryllium. The SCAILD method goes beyond the harmonic approximation to include phonon-phonon interactions and produces a temperature-dependent phonon dispersion. In the high temperature bcc structure, phonon-phonon interactions dynamically stabilize the N-point phonon. Fits to the calculated phonon dispersion were used to determine the temperature dependence of the elastic constants in the hcp and bcc phases. Work at the Ames Laboratory was supported by the Department of Energy-Basic Energy Sciences under Contract No. DE-AC02-07CH11358.

Velocity statistics for interacting edge dislocations in one dimension from Dyson's Coulomb gas model.

PubMed

Jafarpour, Farshid; Angheluta, Luiza; Goldenfeld, Nigel

2013-10-01

The dynamics of edge dislocations with parallel Burgers vectors, moving in the same slip plane, is mapped onto Dyson's model of a two-dimensional Coulomb gas confined in one dimension. We show that the tail distribution of the velocity of dislocations is power law in form, as a consequence of the pair interaction of nearest neighbors in one dimension. In two dimensions, we show the presence of a pairing phase transition in a system of interacting dislocations with parallel Burgers vectors. The scaling exponent of the velocity distribution at effective temperatures well below this pairing transition temperature can be derived from the nearest-neighbor interaction, while near the transition temperature, the distribution deviates from the form predicted by the nearest-neighbor interaction, suggesting the presence of collective effects.

Influence of extreme low temperature conditions on the dynamic mechanical properties of carbon fiber reinforced polymers

NASA Astrophysics Data System (ADS)

Zaoutsos, S. P.; Zilidou, M. C.

2017-12-01

In the current study dynamic mechanical analysis (DMA) is performed in CFRPs that have been exposed for certain periods of time to extreme low temperatures. Through experimental data arising from respective DMA tests the influence of low temperature exposure (-40 °C) on the dynamic mechanical properties is studied. DMA tests were conducted in CFRP specimens in three point bending mode at both frequency and thermal scans in order to determine the viscoelastic response of the material in low temperatures. All experimental tests were run both for aged and pristine materials for comparison purposes. The results occurred reveal that there is deterioration both on transition temperature (Tg) and storage modulus values while there is also a moderate increase in the damping ability of the tested material as expressed by the factor tanδ as the period of exposure to low temperature increases.

Molecular driving forces behind the tetrahydrofuran–water miscibility gap

DOE PAGES

Smith, Micholas Dean; Mostofian, Barmak; Petridis, Loukas; ...

2016-01-06

The tetrahydrofuran water binary system exhibits an unusual closed-loop miscibility gap (transitions from a miscible regime to an immiscible regime back to another miscible regime as the temperature increases). Here, using all-atom molecular dynamics simulations, we probe the structural and dynamical behavior of the binary system in the temperature regime of this gap at four different mass ratios, and we compare the behavior of bulk water and tetrahydrofuran. The changes in structure and dynamics observed in the simulations indicate that the temperature region associated with the miscibility gap is distinctive. Within the miscibility-gap temperature region, the self diffusion of watermore » is significantly altered and the second virial coefficients (pair interaction strengths) show parabolic-like behavior. Altogether, the results suggest that the gap is the result of differing trends with temperature of minor structural changes, which produces interaction virials with parabolic temperature dependence near the miscibility gap.« less

Nature of the octahedral tilting phase transitions in perovskites: A case study of CaMnO3

NASA Astrophysics Data System (ADS)

Klarbring, Johan; Simak, Sergei I.

2018-01-01

The temperature-induced antiferrodistortive (AFD) structural phase transitions in CaMnO3, a typical perovskite oxide, are studied using first-principles density functional theory calculations. These transitions are caused by tilting of the MnO6 octahedra that are related to unstable phonon modes in the high-symmetry cubic perovskite phase. Transitions due to octahedral tilting in perovskites normally are believed to fit into the standard soft-mode picture of displacive phase transitions. We calculate phonon-dispersion relations and potential-energy landscapes as functions of the unstable phonon modes and argue based on the results that the phase transitions are better described as being of order-disorder type. This means that the cubic phase emerges as a dynamical average when the system hops between local minima on the potential-energy surface. We then perform ab initio molecular dynamics simulations and find explicit evidence of the order-disorder dynamics in the system. Our conclusions are expected to be valid for other perovskite oxides, and we finally suggest how to predict the nature (displacive or order-disorder) of the AFD phase transitions in any perovskite system.

Effects of temperature and void on the dynamics and microstructure of structural transition in single crystal iron

NASA Astrophysics Data System (ADS)

Shao, Jian-Li; Wang, Pei; Zhang, Feng-Guo; He, An-Min

2018-06-01

With classic molecular dynamics simulations, we investigate the effects of temperature and void on the bcc to hcp/fcc structural transition in single crystal iron driven by 1D ([0 0 1]) and 3D (uniform) compressions. The results show that the pressure threshold does not reduce monotonously with temperature. The pressure threshold firstly increases and then decreases in the range of 60–360 K under 1D compression, while the variation trend is just opposite under 3D compression. As expected, the initial defect may lower the pressure threshold via heterogenous nucleation. This effect is found to be more distinct at lower temperature, and the heterogenous nucleation mainly results in hcp structure. Under the condition of strain constraint, the products of structural transition will respectively form flaky hcp twin structure ((1 0 0) or (0 1 0)) and lamellar structure ({1 1 0}) of mixed phases under 1D and 3D compressions. During the structural transition, we find the shear stress (1D compression) of hcp phase is always lower than that of bcc phase. The cold energy calculations indicate that the hcp phase is the most stable under high pressure. However, we observe the evident metastable state of bcc phase, whose energy will be much higher than both hcp and fcc phases, and then provides the possibility for the occurrence of fcc nucleation.

Holographic entropy and real-time dynamics of quarkonium dissociation in non-Abelian plasma

DOE PAGES

Iatrakis, Ioannis; Kharzeev, Dmitri E.

2016-04-26

The peak of the heavy quark pair entropy at the deconfinement transition, observed in lattice QCD, suggests that the transition is effectively driven by the increase of the entropy of bound states. The growth of the entropy with the interquark distance leads to the emergent entropic force that induces dissociation of quarkonium states. Since the quark-gluon plasma around the transition point is a strongly coupled system, we use the gauge-gravity duality to study the entropy of heavy quarkonium and the real-time dynamics of its dissociation. In particular, we employ the improved holographic QCD model as a dual description of largemore » N c Yang-Mills theory. Studying the dynamics of the fundamental string between the quarks placed on the boundary, we find that the entropy peaks at the transition point. We also study the real-time dynamics of the system by considering the holographic string falling in the black hole horizon where it equilibrates. As a result, in the vicinity of the deconfinement transition, the dissociation time is found to be less than a fermi, suggesting that the entropic destruction is the dominant dissociation mechanism in this temperature region.« less

Mobility propagation and dynamic facilitation in superionic conductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Annamareddy, Ajay, E-mail: vkannama@ncsu.edu; Eapen, Jacob, E-mail: jacob.eapen@ncsu.edu

2015-11-21

In an earlier work [V. A. Annamareddy et al., Phys. Rev. E 89, 010301(R) (2014)], we showed the manifestation of dynamical heterogeneity (DH)—the presence of clustered mobile and immobile regions—in UO{sub 2}, a model type II superionic conductor. In the current work, we demonstrate the mechanism of dynamic facilitation (DF) in two superionic conductors (CaF{sub 2} and UO{sub 2}) using atomistic simulations. Using the mobility transfer function, DF is shown to vary non-monotonically with temperature with the intensity of DF peaking at temperatures close to the superionic transition temperature (T{sub λ}). Both the metrics quantifying DH and DF show remarkablemore » correspondence implying that DF, in the framework of kinematically constrained models, underpins the heterogeneous dynamics in type II superionic conductors.« less

ESR and PALS detection of the dynamic crossover in the supercooled liquid states of short and medium-sized n-alkanes

NASA Astrophysics Data System (ADS)

Bartoš, J.; Zgardzinska, B.; Švajdlenková, H.; Lukešová, M.; Zaleski, R.

2018-05-01

A joint study of the spin probe TEMPO dynamics by ESR and the annihilation rate of ortho-positronium by PALS in four short-and medium-sized n-alkanes is presented. In addition to the usually observed changes in both the reorientation dynamics and size of free volumes at the temperature of melting, Tm, and solid-solid phase transition, Tss, an additional coincidence between the characteristic ESR and PALS temperatures TX1fast ≅ Tb1sol < Tm, Tss was found. The phenomenological analysis of the viscosity data of n-alkanes using the power law equation indicates a presence of locally disordered regions in which the dynamic change occurs at the crossover temperature TX ≅ TX1fast ≅ Tb1sol.

Dynamical properties in supercooling liquid of trehalose aqueous solution studied by Brillouin scattering

NASA Astrophysics Data System (ADS)

Shibata, Tomohiko; Tominaga, Ayane; Takayama, Haruki; Kojima, Seiji

2013-02-01

Brillouin scattering spectroscopy has been applied to study the dynamical properties of glass transition of trehalose aqueous solutions in a high-frequency gigahertz range and in the temperature range (-190°C ≤ T ≤ 100°C). The temperature variations of sound velocity and attenuation were accurately determined using the refractive index measured by a prism-coupling method. The temperature dependence of relaxation time of the structural relaxation process was determined by the Debye model. Its temperature dependence shows Arrhenius behavior in a liquid state. The parameters of Arrhenius law were also determined as a function of trehalose concentration.

Pairing transition, coherence transition, and the irreversibility line in granular GdBa2Cu3O7-δ

NASA Astrophysics Data System (ADS)

Roa-Rojas, J.; Menegotto Costa, R.; Pureur, P.; Prieto, P.

2000-05-01

We report on electrical magnetoconductivity experiments near the superconducting transition of a granular sample of GdBa2Cu3O7-δ. The measurements were performed in magnetic fields ranging from 0 to 500 Oe applied parallel to the current orientation. The results show that the transition proceeds in two steps. When the temperature is decreased we first observe the pairing transition, which stabilizes superconductivity within the grains at a temperature practically coincident with the bulk critical temperature Tc. Analysis of the fluctuation contributions to the conductivity shows that the universality class for this transition is that of the three dimensional (3D)-XY model in the ordered case, with dynamic critical exponent z=3/2. Close to the zero-resistance state, the measurements reveal the occurrence of a coherence transition, where the phases of the order parameter in individual grains become long-range ordered. The critical temperature Tco for this transition is close to the point where the resistivity vanishes. A strong enlargement of the fluctuation interval preceding the coherence transition is caused by the applied magnetic field. In this region, a 3D-Gaussian regime and an asymptotic critical regime were clearly identified. The critical conductivity behavior for the coherence transition is interpreted within a 3D-XY model where disorder and frustration are relevant. The irreversibility line is determined from magnetoconductivity measurements performed according to the zero-field-cooled (ZFC) and field-cooled data collected on cooling (FCC) recipes. The locus of this line coincides with the upper temperature limit for the fluctuation region above the coherence transition. The irreversibility line is interpreted as an effect of the formation of small clusters with closed loops of Josephson-coupled grains.

Effect of water phase transition on dynamic ruptures with thermal pressurization: Numerical simulations with changes in physical properties of water

NASA Astrophysics Data System (ADS)

Urata, Yumi; Kuge, Keiko; Kase, Yuko

2015-02-01

Phase transitions of pore water have never been considered in dynamic rupture simulations with thermal pressurization (TP), although they may control TP. From numerical simulations of dynamic rupture propagation including TP, in the absence of any water phase transition process, we predict that frictional heating and TP are likely to change liquid pore water into supercritical water for a strike-slip fault under depth-dependent stress. This phase transition causes changes of a few orders of magnitude in viscosity, compressibility, and thermal expansion among physical properties of water, thus affecting the diffusion of pore pressure. Accordingly, we perform numerical simulations of dynamic ruptures with TP, considering physical properties that vary with the pressure and temperature of pore water on a fault. To observe the effects of the phase transition, we assume uniform initial stress and no fault-normal variations in fluid density and viscosity. The results suggest that the varying physical properties decrease the total slip in cases with high stress at depth and small shear zone thickness. When fault-normal variations in fluid density and viscosity are included in the diffusion equation, they activate TP much earlier than the phase transition. As a consequence, the total slip becomes greater than that in the case with constant physical properties, eradicating the phase transition effect. Varying physical properties do not affect the rupture velocity, irrespective of the fault-normal variations. Thus, the phase transition of pore water has little effect on dynamic ruptures. Fault-normal variations in fluid density and viscosity may play a more significant role.

Transport properties of glass-forming liquids suggest that dynamic crossover temperature is as important as the glass transition temperature.

PubMed

Mallamace, Francesco; Branca, Caterina; Corsaro, Carmelo; Leone, Nancy; Spooren, Jeroen; Chen, Sow-Hsin; Stanley, H Eugene

2010-12-28

It is becoming common practice to partition glass-forming liquids into two classes based on the dependence of the shear viscosity η on temperature T. In an Arrhenius plot, ln η vs 1/T, a strong liquid shows linear behavior whereas a fragile liquid exhibits an upward curvature [super-Arrhenius (SA) behavior], a situation customarily described by using the Vogel-Fulcher-Tammann law. Here we analyze existing data of the transport coefficients of 84 glass-forming liquids. We show the data are consistent, on decreasing temperature, with the onset of a well-defined dynamical crossover η(×), where η(×) has the same value, η(×) ≈ 10(3) Poise, for all 84 liquids. The crossover temperature, T(×), located well above the calorimetric glass transition temperature T(g), marks significant variations in the system thermodynamics, evidenced by the change of the SA-like T dependence above T(×) to Arrhenius behavior below T(×). We also show that below T(×) the familiar Stokes-Einstein relation D/T ∼ η(-1) breaks down and is replaced by a fractional form D/T ∼ η(-ζ), with ζ ≈ 0.85.

Transport properties of glass-forming liquids suggest that dynamic crossover temperature is as important as the glass transition temperature

PubMed Central

Mallamace, Francesco; Branca, Caterina; Corsaro, Carmelo; Leone, Nancy; Spooren, Jeroen; Chen, Sow-Hsin; Stanley, H. Eugene

2010-01-01

It is becoming common practice to partition glass-forming liquids into two classes based on the dependence of the shear viscosity η on temperature T. In an Arrhenius plot, ln η vs 1/T, a strong liquid shows linear behavior whereas a fragile liquid exhibits an upward curvature [super-Arrhenius (SA) behavior], a situation customarily described by using the Vogel–Fulcher–Tammann law. Here we analyze existing data of the transport coefficients of 84 glass-forming liquids. We show the data are consistent, on decreasing temperature, with the onset of a well-defined dynamical crossover η×, where η× has the same value, η× ≈ 103 Poise, for all 84 liquids. The crossover temperature, T×, located well above the calorimetric glass transition temperature Tg, marks significant variations in the system thermodynamics, evidenced by the change of the SA-like T dependence above T× to Arrhenius behavior below T×. We also show that below T× the familiar Stokes–Einstein relation D/T ∼ η-1 breaks down and is replaced by a fractional form D/T ∼ η-ζ, with ζ ≈ 0.85. PMID:21148100

The glass and jamming transitions in dense granular matter

NASA Astrophysics Data System (ADS)

Coulais, Corentin; Candelier, Raphaël; Dauchot, Olivier

2013-06-01

Everyday life tells us that matter acquires rigidity either when it cools down, like lava flows which turn into solid rocks, or when it is compacted, like tablets simply formed by powder compression. As suggested by these examples, solidification is not the sole privilege of crystals but also happens for disordered media such as glass formers, granular media, foams, emulsions and colloidal suspensions. Fifteen years ago the "Jamming paradigm" emerged to encompass in a unique framework the glass transition and the emergence of yield stress, two challenging issues in modern condensed matter physics. One must realize how bold this proposal was, given that the glass transition is a finite temperature transition governing the dynamical properties of supercooled liquids, while Jamming is essentially a zero temperature, zero external stress and purely geometric transition which occurs when a given packing of particles reaches the maximum compression state above which particles start to overlap. More recently, the observation of remarkable scaling properties on the approach to jamming led to the conjecture that this zero temperature "critical point" could determine the properties of dense particle systems within a region of the parameter space to be determined, which in principle could include thermal and stressed systems. Fifteen years of intense theoretical and experimental work later, what have we learned about Jamming and glassy dynamics? In this paper, we discuss these issues in the light of the experiments we have been conducting with vibrated grains.

Quantum Griffiths singularity of superconductor-metal transition in Ga thin films.

PubMed

Xing, Ying; Zhang, Hui-Min; Fu, Hai-Long; Liu, Haiwen; Sun, Yi; Peng, Jun-Ping; Wang, Fa; Lin, Xi; Ma, Xu-Cun; Xue, Qi-Kun; Wang, Jian; Xie, X C

2015-10-30

The Griffiths singularity in a phase transition, caused by disorder effects, was predicted more than 40 years ago. Its signature, the divergence of the dynamical critical exponent, is challenging to observe experimentally. We report the experimental observation of the quantum Griffiths singularity in a two-dimensional superconducting system. We measured the transport properties of atomically thin gallium films and found that the films undergo superconductor-metal transitions with increasing magnetic field. Approaching the zero-temperature quantum critical point, we observed divergence of the dynamical critical exponent, which is consistent with the Griffiths singularity behavior. We interpret the observed superconductor-metal quantum phase transition as the infinite-randomness critical point, where the properties of the system are controlled by rare large superconducting regions. Copyright © 2015, American Association for the Advancement of Science.

Dynamic phase diagram of a nonionic surfactant lamellar phase.

PubMed

Gentile, Luigi; Behrens, Manja A; Balog, Sandor; Mortensen, Kell; Ranieri, Giuseppe A; Olsson, Ulf

2014-04-03

The dynamic phase diagram of triethylene glycol dodecyl ether (C12E3) in D2O was determined for 40, 50, and 60 wt % of surfactant. The shear flow effect on the nonionic lamellar phase was investigated as a function of temperature and concentration. The transition from planar lamellae (Lα)-to-multilamellar vesicles (MLVs) was characterized by means of rheology, rheo-small-angle neutron and light scattering. New insight into the nature of the transition region between Lα and the MLVs state is provided. A disorder-order transition was also observed by SANS. This is attributed to a transition from disordered MLVs to a close-packed array of MLV's with slightly higher order than before. Moreover flow instability was observed in the shear-thickening regime at 40 °C.

Lattice dynamics and the nature of structural transitions in organolead halide perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Comin, Riccardo; Crawford, Michael K.; Said, Ayman H.

Organolead halide perovskites are a family of hybrid organic-inorganic compounds whose remarkable optoelectronic properties have been under intensive scrutiny in recent years. Here we use inelastic x-ray scattering to study low-energy lattice excitations in single crystals of methylammonium lead iodide and bromide perovskites. Our findings confirm the displacive nature of the cubic-to-tetragonal phase transition, which is further shown, using neutron and x-ray diffraction, to be close to a tricritical point. Lastly, we detect quasistatic symmetry-breaking nanodomains persisting well into the high-temperature cubic phase, possibly stabilized by local defects. These findings reveal key structural properties of these materials, and also bearmore » important implications for carrier dynamics across an extended temperature range relevant for photovoltaic applications.« less

Two Glass Transitions Associated to Different Dynamic Disorders in the Nematic Glassy State of a Non-Symmetric Liquid Crystal Dimer Dopped with γ-Alumina Nanoparticles

PubMed Central

Diez-Berart, Sergio; López, David O.; Salud, Josep; Diego, José Antonio; Sellarès, Jordi; Robles-Hernández, Beatriz; de la Fuente, María Rosario; Ros, María Blanca

2015-01-01

In the present work, the nematic glassy state of the non-symmetric LC dimer α-(4-cyanobiphenyl-4′-yloxy)-ω-(1-pyrenimine-benzylidene-4′-oxy) undecane is studied by means of calorimetric and dielectric measurements. The most striking result of the work is the presence of two different glass transition temperatures: one due to the freezing of the flip-flop motions of the bulkier unit of the dimer and the other, at a lower temperature, related to the freezing of the flip-flop and precessional motions of the cyanobiphenyl unit. This result shows the fact that glass transition is the consequence of the freezing of one or more coupled dynamic disorders and not of the disordered phase itself. In order to avoid crystallization when the bulk sample is cooled down, the LC dimer has been confined via the dispersion of γ-alumina nanoparticles, in several concentrations.

Dynamics of glass-forming di-n-butyl phthalate as studied by NMR.

PubMed

Szcześniak, E; Głowinkowski, S; Suchański, W; Jurga, S

1997-04-01

Spin-lattice relaxation times T1 and nuclear Overhauser effect (NOE) enhancement factors for the individual ring carbons in di-n-butyl phthalate (DBF) show that the reorientational correlation function corresponding to the global dynamics in supercooled liquid can be described by a Davidson-Cole distribution. Measurements of proton spin-lattice relaxation times T1 and T1p, as well as 1H NMR spectra at temperatures below the glass transition temperature, Tg, reveal that the same distribution holds also for description of local dynamics in glassy DBF. The activation parameters of the motions detected are derived.

Phase transitions and dynamics of bulk and interfacial water.

PubMed

Franzese, G; Hernando-Martínez, A; Kumar, P; Mazza, M G; Stokely, K; Strekalova, E G; de los Santos, F; Stanley, H E

2010-07-21

New experiments on water at the surface of proteins at very low temperature display intriguing dynamic behaviors. The extreme conditions of these experiments make it difficult to explore the wide range of thermodynamic state points needed to offer a suitable interpretation. Detailed simulations suffer from the same problem, where equilibration times at low temperature become extremely long. We show how Monte Carlo simulations and mean field calculations using a tractable model of water help interpret the experimental results. Here we summarize the results for bulk water and investigate the thermodynamic and dynamic properties of supercooled water at an interface.

Universality of the helimagnetic transition in cubic chiral magnets: Small angle neutron scattering and neutron spin echo spectroscopy studies of FeCoSi

NASA Astrophysics Data System (ADS)

Bannenberg, L. J.; Kakurai, K.; Falus, P.; Lelièvre-Berna, E.; Dalgliesh, R.; Dewhurst, C. D.; Qian, F.; Onose, Y.; Endoh, Y.; Tokura, Y.; Pappas, C.

2017-04-01

We present a comprehensive small angle neutron scattering and neutron spin echo spectroscopy study of the structural and dynamical aspects of the helimagnetic transition in Fe1 -xCoxSi with x =0.30 . In contrast to the sharp transition observed in the archetype chiral magnet MnSi, the transition in Fe1 -xCoxSi is gradual, and long-range helimagnetic ordering coexists with short-range correlations over a wide temperature range. The dynamics are more complex than in MnSi and involve long relaxation times with a stretched exponential relaxation which persists even under magnetic field. These results in conjunction with an analysis of the hierarchy of the relevant length scales show that the helimagnetic transition in Fe1 -xCoxSi differs substantially from the transition in MnSi and question the validity of a universal approach to the helimagnetic transition in chiral magnets.

Mixed state dynamical quantum phase transitions

NASA Astrophysics Data System (ADS)

Bhattacharya, Utso; Bandyopadhyay, Souvik; Dutta, Amit

2017-11-01

Preparing an integrable system in a mixed state described by a thermal density matrix, we subject it to a sudden quench and explore the subsequent unitary dynamics. To address the question of whether the nonanalyticities, namely, the dynamical quantum phase transitions (DQPTs), persist when the initial state is mixed, we consider two versions of the generalized Loschmidt overlap amplitude (GLOA). Our study shows that the GLOA constructed using the Uhlmann approach does not show any signature of DQPTs at any nonzero initial temperature. On the other hand, a GLOA defined in the interferometric phase approach through the purifications of the time-evolved density matrix, indeed shows that nonanalyiticies in the corresponding "dynamical free-energy density" persist, thereby establishing the existence of mixed state dynamical quantum phase transitions (MSDQPTs). Our work provides a framework that perfectly reproduces both the nonanalyticities and also the emergent topological structure in the pure state limit. These claims are corroborated by analyzing the nonequilibrium dynamics of a transverse Ising chain initially prepared in a thermal state and subjected to a sudden quench of the transverse field.

Dynamic phase transitions and dynamic phase diagrams of the Blume-Emery-Griffiths model in an oscillating field: the effective-field theory based on the Glauber-type stochastic dynamics

NASA Astrophysics Data System (ADS)

Ertaş, Mehmet; Keskin, Mustafa

2015-06-01

Using the effective-field theory based on the Glauber-type stochastic dynamics (DEFT), we investigate dynamic phase transitions and dynamic phase diagrams of the Blume-Emery-Griffiths model under an oscillating magnetic field. We presented the dynamic phase diagrams in (T/J, h0/J), (D/J, T/J) and (K/J, T/J) planes, where T, h0, D, K and z are the temperature, magnetic field amplitude, crystal-field interaction, biquadratic interaction and the coordination number. The dynamic phase diagrams exhibit several ordered phases, coexistence phase regions and special critical points, as well as re-entrant behavior depending on interaction parameters. We also compare and discuss the results with the results of the same system within the mean-field theory based on the Glauber-type stochastic dynamics and find that some of the dynamic first-order phase lines and special dynamic critical points disappeared in the DEFT calculation.

Electronic excitation induced amorphization in titanate pyrochlores: an ab initio molecular dynamics study

PubMed Central

Xiao, H. Y.; Weber, W. J.; Zhang, Y.; Zu, X. T.; Li, S.

2015-01-01

The response of titanate pyrochlores (A2Ti2O7, A = Y, Gd and Sm) to electronic excitation is investigated utilizing an ab initio molecular dynamics method. All the titanate pyrochlores are found to undergo a crystalline-to-amorphous structural transition under a low concentration of electronic excitations. The transition temperature at which structural amorphization starts to occur depends on the concentration of electronic excitations. During the structural transition, O2-like molecules are formed, and this anion disorder further drives cation disorder that leads to an amorphous state. This study provides new insights into the mechanisms of amorphization in titanate pyrochlores under laser, electron and ion irradiations. PMID:25660219

Multiscale Relaxation Dynamics in Ultrathin Metallic Glass-Forming Films

NASA Astrophysics Data System (ADS)

Bi, Q. L.; Lü, Y. J.; Wang, W. H.

2018-04-01

The density layering phenomenon originating from a free surface gives rise to the layerlike dynamics and stress heterogeneity in ultrathin Cu-Zr glassy films, which facilitates the occurrence of multistep relaxations in the timescale of computer simulations. Taking advantage of this condition, we trace the relaxation decoupling and evolution with temperature simply via the intermediate scattering function. We show that the β relaxation hierarchically follows fast and slow modes in films, and there is a β -relaxation transition as the film is cooled close to the glass transition. We provide the direct observation of particle motions responsible for the β relaxation and reveal the dominant mechanism varying from the thermal activated to the cooperative jumps across the transition.

Electronic excitation induced amorphization in titanate pyrochlores: an ab initio molecular dynamics study.

PubMed

Xiao, H Y; Weber, W J; Zhang, Y; Zu, X T; Li, S

2015-02-09

The response of titanate pyrochlores (A2Ti2O7, A = Y, Gd and Sm) to electronic excitation is investigated utilizing an ab initio molecular dynamics method. All the titanate pyrochlores are found to undergo a crystalline-to-amorphous structural transition under a low concentration of electronic excitations. The transition temperature at which structural amorphization starts to occur depends on the concentration of electronic excitations. During the structural transition, O2-like molecules are formed, and this anion disorder further drives cation disorder that leads to an amorphous state. This study provides new insights into the mechanisms of amorphization in titanate pyrochlores under laser, electron and ion irradiations.

Relaxation processes and glass transition of confined polymer melts: A molecular dynamics simulation of 1,4-polybutadiene between graphite walls.

PubMed

Solar, M; Binder, K; Paul, W

2017-05-28

Molecular dynamics simulations of a chemically realistic model for 1,4-polybutadiene in a thin film geometry confined by two graphite walls are presented. Previous work on melts in the bulk has shown that the model faithfully reproduces static and dynamic properties of the real material over a wide temperature range. The present work studies how these properties change due to nano-confinement. The focus is on orientational correlations observable in nuclear magnetic resonance experiments and on the local intermediate incoherent neutron scattering function, F s (q z , z, t), for distances z from the graphite walls in the range of a few nanometers. Temperatures from about 2T g down to about 1.15T g , where T g is the glass transition temperature in the bulk, are studied. It is shown that weakly attractive forces between the wall atoms and the monomers suffice to effectively bind a polymer coil that is near the wall. For a wide regime of temperatures, the Arrhenius-like adsorption/desorption kinetics of the monomers is the slowest process, while very close to T g the Vogel-Fulcher-Tammann-like α-relaxation takes over. The α-process is modified only for z≤1.2 nm due to the density changes near the walls, less than expected from studies of coarse-grained (bead-spring-type) models. The weakness of the surface effects on the glass transition in this case is attributed to the interplay of density changes near the wall with the torsional potential. A brief discussion of pertinent experiments is given.

Holographic QCD phase diagram with critical point from Einstein-Maxwell-dilaton dynamics

NASA Astrophysics Data System (ADS)

Knaute, J.; Yaresko, R.; Kämpfer, B.

2018-03-01

Supplementing the holographic Einstein-Maxwell-dilaton model of [1,2] by input of lattice QCD data for 2 + 1 flavors and physical quark masses for the equation of state and quark number susceptibility at zero baryo-chemical potential we explore the resulting phase diagram over the temperature-chemical potential plane. A first-order phase transition sets in at a temperature of about 112 MeV and a baryo-chemical potential of 612 MeV. We estimate the accuracy of the critical point position in the order of approximately 5-8% by considering parameter variations and different low-temperature asymptotics for the second-order quark number susceptibility. The critical pressure as a function of the temperature has a positive slope, i.e. the entropy per baryon jumps up when crossing the phase border line from larger values of temperature/baryo-chemical potential, thus classifying the phase transition as a gas-liquid one. The updated holographic model exhibits in- and outgoing isentropes in the vicinity of the first-order phase transition.

Glass-Transition Temperature of the β-Relaxation as the Major Predictive Parameter for Recrystallization of Neat Amorphous Drugs.

PubMed

Kissi, Eric Ofosu; Grohganz, Holger; Löbmann, Korbinian; Ruggiero, Michael T; Zeitler, J Axel; Rades, Thomas

2018-03-15

Recrystallization of amorphous drugs is currently limiting the simple approach to improve solubility and bioavailability of poorly water-soluble drugs by amorphization of a crystalline form of the drug. In view of this, molecular mobility, α-relaxation and β-relaxation processes with the associated transition temperatures T gα and T gβ , was investigated using dynamic mechanical analysis (DMA). The correlation between the transition temperatures and the onset of recrystallization for nine amorphous drugs, stored under dry conditions at a temperature of 296 K, was determined. From the results obtained, T gα does not correlate with the onset of recrystallization under the experimental storage conditions. However, a clear correlation between T gβ and the onset of recrystallization was observed. It is shown that at storage temperature below T gβ , amorphous nifedipine retains its amorphous form. On the basis of the correlation, an empirical correlation is proposed for predicting the onset of recrystallization for drugs stored at 0% RH and 296 K.

Temperature dependence of the fundamental optical absorption edge in crystals and disordered semiconductors

NASA Astrophysics Data System (ADS)

Grein, C. H.; John, Sajeev

1989-04-01

We present a first principles theory of the temperature dependence of the Urbach optical absorption edge in crystals and disordered semiconductors which incorporates the effects of short range correlated static disorder and the non-adiabatic quantum dynamics of the coupled electron-phonon system. At finite temperatures the dominant features of the Urbach tail are accounted for by multiple phonon absorption and emission side bands which accompany the optically induced electronic transition and which provide a dynamic polaronic potential well that localizes the electron. Excellent agreement is found with experimental data on both crystalline and amorphous silicon.

Temperature-dependent solubility transition of Na₂SO₄ in water and the effect of NaCl therein: solution structures and salt water dynamics.

PubMed

Bharmoria, Pankaj; Gehlot, Praveen Singh; Gupta, Hariom; Kumar, Arvind

2014-11-06

Dual, aqueous solubility behavior of Na2SO4 as a function of temperatures is still a natural enigma lying unresolved in the literature. The solubility of Na2SO4 increases up to 32.38 °C and decreases slightly thereafter at higher temperatures. We have thrown light on this phenomenon by analyzing the Na2SO4-water clusters (growth and stability) detected from temperature-dependent dynamic light scattering experiments, solution compressibility changes derived from the density and speed of sound measurements, and water structural changes/Na2SO4 (ion pair)-water interactions observed from the FT-IR and 2D DOSY (1)H NMR spectroscopic investigations. It has been observed that Na2SO4-water clusters grow with an increase in Na2SO4 concentration (until the solubility transition temperature) and then start decreasing afterward. An unusual decrease in cluster size and solution compressibility has been observed with the rise in temperature for the Na2SO4 saturated solutions below the solubility transition temperature, whereas an inverse pattern is followed thereafter. DOSY experiments have indicated different types of water cluster species in saturated solutions at different temperatures with varying self-diffusion coefficients. The effect of NaCl (5-15 wt %) on the solubility behavior of Na2SO4 at different temperatures has also been examined. The studies are important from both fundamental and industrial application points of view, for example, toward the clean separation of NaCl and Na2SO4 from the effluent streams of textile and tannery industries.

Bond-length fluctuations and the spin-state transition in LCoO3 (L=La, Pr, and Nd)

NASA Astrophysics Data System (ADS)

Yan, J.-Q.; Zhou, J.-S.; Goodenough, J. B.

2004-04-01

The temperature dependence of thermal conductivity, κ(T), and magnetic susceptibility, χ(T), have been measured on single crystals of LCoO3 (L=La, Pr, Nd) grown by the floating-zone method. The susceptibility measurement shows a progressive stabilization of the low-spin (LS) state of Co(III) with decreasing size of the L3+ ion, and the population of excited intermediate-spin (IS) or high-spin (HS) state Co(III) ions begins to increase at 200 K and 300 K for PrCoO3 and NdCoO3 compared with 35 K in LaCoO3. The low-temperature Curie-Weiss paramagnetic susceptibility of LCoO3 is an intrinsic property arising from surface cobalt and, possibly, a LS ground state bearing some IS character caused by the virtual excitation to the IS state. The transition from a LS to a IS/HS state introduces bond-length fluctuations that suppress the phonon contribution to κ(T) below 300 K. The suppressed κ(T) could be further reduced by dynamic Jahn-Teller distortions associated with the IS/HS species. A smooth transition in ρ(T) and α(T) and a nearly temperature independent α(T)≈20 μV/K above 600 K do not support a thermally induced, homogeneous Mott-Hubbard transition model for the high-temperature transition of LaCoO3 from an insulating to a conductive state. A two-phase process is proposed for the interval 300 K

Rigidity and soft percolation in the glass transition of an atomistic model of ionic liquid, 1-ethyl-3-methyl imidazolium nitrate, from molecular dynamics simulations—Existence of infinite overlapping networks in a fragile ionic liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Habasaki, Junko, E-mail: habasaki.j.aa@m.titech.ac.jp; Ngai, K. L.

The typical ionic liquid, 1-ethyl-3-methyl imidazolium nitrate (EMIM-NO{sub 3}), was examined by molecular dynamics simulations of an all-atomistic model to show the characteristics of networks of cages and/or bonds in the course of vitrification of this fragile glass-former. The system shows changes of dynamics at two characteristic temperatures, T{sub B} (or T{sub c}) and the glass transition temperature T{sub g}, found in other fragile glass forming liquids [K. L. Ngai and J. Habasaki, J. Chem. Phys. 141, 114502 (2014)]. On decreasing temperature, the number of neighboring cation-anion pairs, N{sub B}, within the first minimum of the pair correlation function, g(r){submore » min}, increases. On crossing T{sub B} (>T{sub g}), the system volume and diffusion coefficient both show changes in temperature dependence, and as usual at T{sub g}. The glass transition temperature, T{sub g}, is characterized by the saturation of the total number of “bonds,” N{sub B} and the corresponding decrease in degree of freedom, F = [(3N − 6) − N{sub B}], of the system consisting of N particles. Similar behavior holds for the other ion-ion pairs. Therefore, as an alternative, the dynamics of glass transition can be interpreted conceptually by rigidity percolation. Before saturation occurring at T{sub g}, the number of bonds shows a remarkable change at around T{sub B}. This temperature is associated with the disappearance of the loosely packed coordination polyhedra of anions around cation (or vice versa), related to the loss of geometrical freedom of the polyhedra, f{sub g}, of each coordination polyhedron, which can be defined by f{sub g} = [(3N{sub V} − 6) − N{sub b}]. Here, 3N{sub v} is the degree of freedom of N{sub V} vertices of the polyhedron, and N{sub b} is number of fictive bonds. The packing of polyhedra is characterized by the soft percolation of cages, which allows further changes with decreasing temperature. The power spectrum of displacement of the central ion in the cage is found to be correlated with the fluctuation of N{sub b} of cation-cation (or anion-anion) pairs in the polyhedron, although the effect from the coordination shells beyond the neighboring ions is not negligible.« less

Predict the glass transition temperature and plasticization of β-cyclodextrin/water binary system by molecular dynamics simulation.

PubMed

Zhou, Guohui; Zhao, Tianhai; Wan, Jie; Liu, Chengmei; Liu, Wei; Wang, Risi

2015-01-12

The glass transition temperature, diffusion behavior and plasticization of β-cyclodextrin (β-CD), and three amorphous β-CD/water mixtures (3%, 5% and 10% [w/w] water, respectively) were investigated by molecular dynamics simulation, which were performed using Condensed-phase Optimized Molecular Potentials for Atomistic Simulation Studies (COMPASS) force field and isothermal-isobaric ensembles. The specific volumes of four amorphous cells were obtained as a function of temperature. The glass transition temperatures (T(g)) were estimated to be 334.25 K, 325.12 K, 317.32 K, and 305.41 K for amorphous β-CD containing 0%, 3%, 5% and 10% w/w water, respectively, which compares well with the values observed in published literature. The radial distribution function was computed to elucidate the intermolecular interactions between amorphous β-CD and water, which acts as a plasticizer. These results indicate that the hydrogen bond interactions of oxygen in hydroxyl ions was higher than oxygen in acetal groups in β-CD amorphous mixtures with that in water, due to less accessibility of ring oxygens to the surrounding water molecules. The mobility of water molecules was investigated over various temperature ranges, including the rubbery and glassy phases of the β-CD/water mixtures, by calculating the diffusion coefficients and the fractional free volume. In β-CD amorphous models, the higher mobility of water molecules was observed at temperatures above Tg, and almost no change was observed at temperatures below T(g). Copyright © 2014 Elsevier Ltd. All rights reserved.

Multiple-basin energy landscapes for large-amplitude conformational motions of proteins: Structure-based molecular dynamics simulations

PubMed Central

Okazaki, Kei-ichi; Koga, Nobuyasu; Takada, Shoji; Onuchic, Jose N.; Wolynes, Peter G.

2006-01-01

Biomolecules often undergo large-amplitude motions when they bind or release other molecules. Unlike macroscopic machines, these biomolecular machines can partially disassemble (unfold) and then reassemble (fold) during such transitions. Here we put forward a minimal structure-based model, the “multiple-basin model,” that can directly be used for molecular dynamics simulation of even very large biomolecular systems so long as the endpoints of the conformational change are known. We investigate the model by simulating large-scale motions of four proteins: glutamine-binding protein, S100A6, dihydrofolate reductase, and HIV-1 protease. The mechanisms of conformational transition depend on the protein basin topologies and change with temperature near the folding transition. The conformational transition rate varies linearly with driving force over a fairly large range. This linearity appears to be a consequence of partial unfolding during the conformational transition. PMID:16877541

Structural γ-ε phase transition in Fe-Mn alloys from a CPA  +  DMFT approach.

PubMed

Belozerov, A S; Poteryaev, A I; Skornyakov, S L; Anisimov, V I

2015-11-25

We present a computational scheme for total energy calculations of disordered alloys with strong electronic correlations. It employs the coherent potential approximation combined with the dynamical mean-field theory and allows one to study the structural transformations. The material-specific Hamiltonians in the Wannier function basis are obtained by density functional theory. The proposed computational scheme is applied to study the γ-ε structural transition in paramagnetic Fe-Mn alloys for Mn content from 10 to 20 at.%. The electronic correlations are found to play a crucial role in this transition. The calculated transition temperature decreases with increasing Mn content and is in good agreement with experiment. We demonstrate that in contrast to the α-γ transition in pure iron, the γ-ε transition in Fe-Mn alloys is driven by a combination of kinetic and Coulomb energies. The latter is found to be responsible for the decrease of the γ-ε transition temperature with Mn content.

Dynamic alterations of hepatocellular function by on-demand elasticity and roughness modulation.

PubMed

Uto, K; Aoyagi, T; DeForest, C A; Ebara, M

2018-05-01

Temperature-responsive cell culture substrates reported here can be dynamically programmed to induce bulk softening and surface roughness changes in the presence of living cells. Alterations in hepatocellular function following temporally controlled substrate softening depend on the extent of stiff mechanical priming prior to user-induced material transition.

Geometry in transition in four dimensions: A model of emergent geometry in the early universe

NASA Astrophysics Data System (ADS)

Ydri, Badis; Khaled, Ramda; Ahlam, Rouag

2016-10-01

We study a six matrix model with global S O (3 )×S O (3 ) symmetry containing at most quartic powers of the matrices. This theory exhibits a phase transition from a geometrical phase at low temperature to a Yang-Mills matrix phase with no background geometrical structure at high temperature. This is an exotic phase transition in the same universality class as the three matrix model but with important differences. The geometrical phase is determined dynamically, as the system cools, and is given by a fuzzy sphere background SN2×SN2, with an Abelian gauge field which is very weakly coupled to two normal scalar fields.

Theory of low transitions in CO discharge lasers

NASA Technical Reports Server (NTRS)

Sidney, B. D.; Mcinuille, R. M.; Smith, N. S.; Hassan, H. A.

1976-01-01

A self consistent theoretical model which couples the electron and heavy particle finite rate kinetics with the optical and fluid dynamic processes has been employed to identify the various parameters and explain the mechanism responsible for producing low lying transitions in slow flowing CO lasers. It is found that lasing on low lying transitions can be achieved at low temperatures for low pressures (or low flow rates) together with high partial pressures of the He and N2. The role of N2 has been identified as an additive responsible for reducing the electron temperature to a range where the transfer of electrical power to the lower vibrational modes of CO is optimum.

Sequence Directionality Dramatically Affects LCST Behavior of Elastin-Like Polypeptides.

PubMed

Li, Nan K; Roberts, Stefan; Quiroz, Felipe Garcia; Chilkoti, Ashutosh; Yingling, Yaroslava G

2018-04-30

Elastin-like polypeptides (ELP) exhibit an inverse temperature transition or lower critical solution temperature (LCST) transition phase behavior in aqueous solutions. In this paper, the thermal responsive properties of the canonical ELP, poly(VPGVG), and its reverse sequence poly(VGPVG) were investigated by turbidity measurements of the cloud point behavior, circular dichroism (CD) measurements, and all-atom molecular dynamics (MD) simulations to gain a molecular understanding of mechanism that controls hysteretic phase behavior. It was shown experimentally that both poly(VPGVG) and poly(VGPVG) undergo a transition from soluble to insoluble in aqueous solution upon heating above the transition temperature ( T t ). However, poly(VPGVG) resolubilizes upon cooling below its T t , whereas the reverse sequence, poly(VGPVG), remains aggregated despite significant undercooling below the T t . The results from MD simulations indicated that a change in sequence order results in significant differences in the dynamics of the specific residues, especially valines, which lead to extensive changes in the conformations of VPGVG and VGPVG pentamers and, consequently, dissimilar propensities for secondary structure formation and overall structure of polypeptides. These changes affected the relative hydrophilicities of polypeptides above T t , where poly(VGPVG) is more hydrophilic than poly(VPGVG) with more extended conformation and larger surface area, which led to formation of strong interchain hydrogen bonds responsible for stabilization of the aggregated phase and the observed thermal hysteresis for poly(VGPVG).

High pressure study of molecular dynamics of protic ionic liquid lidocaine hydrochloride.

PubMed

Swiety-Pospiech, A; Wojnarowska, Z; Pionteck, J; Pawlus, S; Grzybowski, A; Hensel-Bielowka, S; Grzybowska, K; Szulc, A; Paluch, M

2012-06-14

In this paper, we investigate the effect of pressure on the molecular dynamics of protic ionic liquid lidocaine hydrochloride, a commonly used pharmaceutical, by means of dielectric spectroscopy and pressure-temperature-volume methods. We observed that near T(g) the pressure dependence of conductivity relaxation times reveals a peculiar behavior, which can be treated as a manifestation of decoupling between ion migration and structural relaxation times. Moreover, we discuss the validity of thermodynamic scaling in lidocaine HCl. We also employed the temperature-volume Avramov model to determine the value of pressure coefficient of glass transition temperature, dT(g)/dP|(P = 0.1). Finally, we investigate the role of thermal and density fluctuations in controlling of molecular dynamics of the examined compound.

Dynamic magnetic hysteresis properties of two-dimensional ferrimagnetic structures containing high-spin (S = 5/2) and low-spin (S = 1/2)

NASA Astrophysics Data System (ADS)

Batı, Mehmet; Ertaş, Mehmet

2017-09-01

The dynamic hysteresis behaviors of a containing high spin-5/2 and low spin-1/2 Ising ferrimagnetic system on a square lattice are studied by using the dynamic mean-field approximation. The influences of the temperature, the single-ion anisotropy and the frequency on dynamic hysteresis behaviors are investigated in detail. Somewhat characteristic behaviors are found, such as the presence of triple hysteresis loop for appropriate values of the crystal field or temperature. Besides, we observed that, hysteresis loop area and phase transition points are very sensitive to changes in frequency and thus have profound importance in device application.

Polymer Dynamics from Synthetic to Biological Macromolecules

NASA Astrophysics Data System (ADS)

Richter, D.; Niedzwiedz, K.; Monkenbusch, M.; Wischnewski, A.; Biehl, R.; Hoffmann, B.; Merkel, R.

2008-02-01

High resolution neutron scattering together with a meticulous choice of the contrast conditions allows to access the large scale dynamics of soft materials including biological molecules in space and time. In this contribution we present two examples. One from the world of synthetic polymers, the other from biomolecules. First, we will address the peculiar dynamics of miscible polymer blends with very different component glass transition temperatures. Polymethylmetacrylate (PMMA), polyethyleneoxide (PEO) are perfectly miscible but exhibit a difference in the glass transition temperature by 200 K. We present quasielastic neutron scattering investigations on the dynamics of the fast component in the range from angströms to nanometers over a time frame of five orders of magnitude. All data may be consistently described in terms of a Rouse model with random friction, reflecting the random environment imposed by the nearly frozen PMMA matrix on the fast mobile PEO. In the second part we touch on some new developments relating to large scale internal dynamics of proteins by neutron spin echo. We will report results of some pioneering studies which show the feasibility of such experiments on large scale protein motion which will most likely initiate further studies in the future.

Distinctly Different Glass Transition Behaviors of Trehalose Mixed with Na2HPO 4 or NaH 2PO 4: Evidence for its Molecular Origin.

PubMed

Weng, Lindong; Elliott, Gloria D

2015-07-01

The present study is aimed at understanding how the interactions between sugar molecules and phosphate ions affect the glass transition temperature of their mixtures, and the implications for pharmaceutical formulations. The glass transition temperature (Tg) and the α-relaxation temperature (Tα) of dehydrated trehalose/sodium phosphate mixtures (monobasic or dibasic) were determined by differential scanning calorimetry and dynamic mechanical analysis, respectively. Molecular dynamics simulations were also conducted to investigate the microscopic interactions between sugar molecules and phosphate ions. The hydrogen-bonding characteristics and the self-aggregation features of these mixtures were quantified and compared. Thermal analysis measurements demonstrated that the addition of NaH2PO4 decreased both the glass transition temperature and the α-relaxation temperature of the dehydrated trehalose/NaH2PO4 mixture compared to trehalose alone while both Tg and Tα were increased by adding Na2HPO4 to pure trehalose. The hydrogen-bonding interactions between trehalose and HPO4(2-) were found to be stronger than both the trehalose-trehalose hydrogen bonds and those formed between trehalose and H2PO4(-). The HPO4(2-) ions also aggregated into smaller clusters than H2PO4(-) ions. The trehalose/Na2HPO4 mixture yielded a higher T g than pure trehalose because marginally self-aggregated HPO4(2-) ions established a strengthened hydrogen-bonding network with trehalose molecules. In contrast H2PO4(-) ions served only as plasticizers, resulting in a lower Tg of the mixtures than trehalose alone, creating large-sized ionic pockets, weakening interactions, and disrupting the original hydrogen-bonding network amongst trehalose molecules.

Distinctly Different Glass Transition Behaviors of Trehalose Mixed with Na2HPO4 or NaH2PO4: Evidence for its Molecular Origin

PubMed Central

Weng, Lindong; Elliott, Gloria D.

2015-01-01

Purpose The present study is aimed at understanding how the interactions between sugar molecules and phosphate ions affect the glass transition temperature of their mixtures, and the implications for pharmaceutical formulations. Methods The glass transition temperature (Tg) and the α-relaxation temperature (Tα) of dehydrated trehalose/sodium phosphate mixtures (monobasic or dibasic) were determined by differential scanning calorimetry and dynamic mechanical analysis, respectively. Molecular dynamics simulations were also conducted to investigate the microscopic interactions between sugar molecules and phosphate ions. The hydrogen-bonding characteristics and the self-aggregation features of these mixtures were quantified and compared. Results Thermal analysis measurements demonstrated that the addition of NaH2PO4 decreased both the glass transition temperature and the α-relaxation temperature of the dehydrated trehalose/NaH2PO4 mixture compared to trehalose alone while both Tg and Tα were increased by adding Na2HPO4 to pure trehalose. The hydrogen-bonding interactions between trehalose and HPO42− were found to be stronger than both the trehalose-trehalose hydrogen bonds and those formed between trehalose and H2PO4−. The HPO42− ions also aggregated into smaller clusters than H2PO4− ions. Conclusions The trehalose/Na2HPO4 mixture yielded a higher Tg than pure trehalose because marginally self-aggregated HPO42− ions established a strengthened hydrogen-bonding network with trehalose molecules. In contrast H2PO4− ions served only as plasticizers, resulting in a lower Tg of the mixtures than trehalose alone, creating large-sized ionic pockets, weakening interactions, and disrupting the original hydrogen-bonding network amongst trehalose molecules. PMID:25537342

Cooperative behavior of molecular motions giving rise to two glass transitions in the same supercooled mesophase of a smectogenic liquid crystal dimer

NASA Astrophysics Data System (ADS)

López, David O.; Salud, Josep; de la Fuente, María Rosario; Sebastián, Nerea; Diez-Berart, Sergio

2018-01-01

In the present work, a detailed analysis of the glassy behavior and the relaxation dynamics of the liquid crystal dimer α-(4-cyanobiphenyl-4'-yloxy)-ω-(1-pyrenimine-benzylidene-4'-oxy) heptane (CBO7O.Py) throughout both nematic and smectic-A mesophases by means of broadband dielectric spectroscopy has been performed. CBO7O.Py shows three different dielectric relaxation modes and two glass transition (Tg) temperatures: The higher Tg is due to the freezing of the molecular motions responsible for the relaxation mode with the lowest frequency (μ1 L); the lower Tg is due to the motions responsible for the two relaxation modes with highest frequencies (μ1 H and μ2), which converge just at their corresponding Tg. It is shown how the three modes follow a critical-like description via the dynamic scaling model. The two modes with lowest frequencies (μ1 L and μ1 H) are cooperative in the whole range of the mesophases, whereas the highest frequency mode (μ2) is cooperative just below some crossover temperature. In terms of fragility, at the glass transition, the ensemble (μ1 H+μ2 ) presents a value of the steepness index and μ1 L a different one, meaning that fragility is a property intrinsic to the molecular motion itself. Finally, the steepness index seems to have a universal behavior with temperature for the dielectric relaxation modes of liquid crystal dimers, being almost constant at high temperatures and increasing drastically when cooling the compound down to the glass transition from a temperature about 3/4 TN I .

Temperature dependence of phonons in photosynthesis proteins

NASA Astrophysics Data System (ADS)

Xu, Mengyang; Myles, Dean; Blankenship, Robert; Markelz, Andrea

Protein long range vibrations are essential to biological function. For many proteins, these vibrations steer functional conformational changes. For photoharvesting proteins, the structural vibrations play an additional critical role in energy transfer to the reaction center by both phonon assisted energy transfer and energy dissipation. The characterization of these vibrations to understand how they are optimized to balance photoharvesting and photoprotection is challenging. To date this characterization has mainly relied on fluorescence line narrowing measurements at cryogenic temperatures. However, protein dynamics has a strong temperature dependence, with an apparent turn on in anharmonicity between 180-220 K. If this transition affects intramolecular vibrations, the low temperature measurements will not represent the phonon spectrum at biological temperatures. Here we use the new technique of anisotropic terahertz microscopy (ATM) to measure the intramolecular vibrations of FMO complex. ATM is uniquely capable of isolating protein vibrations from isotropic background. We find resonances both red and blue shift with temperature above the dynamical transition. The results indicate that the characterization of vibrations must be performed at biologically relevant temperatures to properly understand the energy overlap with the excitation energy transfer. This work was supported by NSF:DBI 1556359, BioXFEL seed Grant funding from NSF:DBI 1231306, DOE: DE-SC0016317, and the Bruce Holm University at Buffalo Research Foundation Grant.

Wetting-Dewetting and Dispersion-Aggregation Transitions Are Distinct for Polymer Grafted Nanoparticles in Chemically Dissimilar Polymer Matrix.

PubMed

Martin, Tyler B; Mongcopa, Katrina Irene S; Ashkar, Rana; Butler, Paul; Krishnamoorti, Ramanan; Jayaraman, Arthi

2015-08-26

Simulations and experiments are conducted on mixtures containing polymer grafted nanoparticles in a chemically distinct polymer matrix, where the graft and matrix polymers exhibit attractive enthalpic interactions at low temperatures that become progressively repulsive as temperature is increased. Both coarse-grained molecular dynamics simulations, and X-ray scattering and neutron scattering experiments with deuterated polystyrene (dPS) grafted silica and poly(vinyl methyl ether) PVME matrix show that the sharp phase transition from (mixed) dispersed to (demixed) aggregated morphologies due to the increasingly repulsive effective interactions between the blend components is distinct from the continuous wetting-dewetting transition. Strikingly, this is unlike the extensively studied chemically identical graft-matrix composites, where the two transitions have been considered to be synonymous, and is also unlike the free (ungrafted) blends of the same graft and matrix homopolymers, where the wetting-dewetting is a sharp transition coinciding with the macrophase separation.

Relaxation dynamics of magnetization transitions in synthetic antiferromagnet with perpendicular anisotropy

NASA Astrophysics Data System (ADS)

Talantsev, A.; Lu, Y.; Fache, T.; Lavanant, M.; Hamadeh, A.; Aristov, A.; Koplak, O.; Morgunov, R.; Mangin, S.

2018-04-01

Two synthetic antiferromagnet bilayer systems with strong perpendicular anisotropy CoFeB/Ta/CoFeB and Pt/Co/Ir/Co/Pt have been grown using sputtering techniques. For both systems two types of magnetization transitions have been studied. The first one concerns transitions from a state where magnetizations of the two magnetic layers are parallel (P state) to a state where magnetizations of the two layers are aligned antiparallel (AP state). The second one concerns transitions between the two possible antiparallel alignments (AP+  to AP-). For both systems and both transitions after-effect measurements can be understood in the frame of nucleation—propagation model. Time derivative analysis of magnetic relaxation curves and mapping of the first order reversal curves at different temperature allowed us to demonstrate the presence of different pinning centers, which number can be controlled by magnetic field and temperature.

Study on the effect of transition curve to the dynamic characteristics of high-temperature superconducting maglev

NASA Astrophysics Data System (ADS)

Qian, Nan; Zheng, Botian; Gou, Yanfeng; Chen, Ping; Zheng, Jun; Deng, Zigang

2015-12-01

High temperature superconducting (HTS) maglev technology is becoming more and more mature, and many key technologies have been deeply studied. However, the transition curve plays a key role in HTS maglev system, and related studies have not been carried out. In this paper series of simulations were conducted to test the lateral and vertical vibration of HTS maglev when passing through curves. Two magnetic guideways, of which one has transition curves but the other does not, are designed to test the vibration characteristics of a mini HTS maglev model running though curves. Results show that after adding transition curves between straight line and circular curve the vibration of HTS maglev model in lateral and vertical directions are all weakened in different degrees. It proves that adding transition curve into HTS maglev system is favorable and necessary.

The α–β phase transition in volcanic cristobalite

PubMed Central

Damby, David E.; Llewellin, Edward W.; Horwell, Claire J.; Williamson, Ben J.; Najorka, Jens; Cressey, Gordon; Carpenter, Michael

2014-01-01

Cristobalite is a common mineral in volcanic ash produced from dome-forming eruptions. Assessment of the respiratory hazard posed by volcanic ash requires understanding the nature of the cristobalite it contains. Volcanic cristobalite contains coupled substitutions of Al3+ and Na+ for Si4+; similar co-substitutions in synthetic cristobalite are known to modify the crystal structure, affecting the stability of the α and β forms and the observed transition between them. Here, for the first time, the dynamics and energy changes associated with the α–β phase transition in volcanic cristobalite are investigated using X-ray powder diffraction with simultaneous in situ heating and differential scanning calorimetry. At ambient temperature, volcanic cristobalite exists in the α form and has a larger cell volume than synthetic α-cristobalite; as a result, its diffraction pattern sits between ICDD α- and β-cristobalite library patterns, which could cause ambiguity in phase identification. On heating from ambient temperature, volcanic cristobalite exhibits a lower degree of thermal expansion than synthetic cristobalite, and it also has a lower α–β transition temperature (∼473 K) compared with synthetic cristobalite (upwards of 543 K); these observations are discussed in relation to the presence of Al3+ and Na+ defects. The transition shows a stable and reproducible hysteresis loop with α and β phases coexisting through the transition, suggesting that discrete crystals in the sample have different transition temperatures. PMID:25242910

The α-β phase transition in volcanic cristobalite.

PubMed

Damby, David E; Llewellin, Edward W; Horwell, Claire J; Williamson, Ben J; Najorka, Jens; Cressey, Gordon; Carpenter, Michael

2014-08-01

Cristobalite is a common mineral in volcanic ash produced from dome-forming eruptions. Assessment of the respiratory hazard posed by volcanic ash requires understanding the nature of the cristobalite it contains. Volcanic cristobalite contains coupled substitutions of Al 3+ and Na + for Si 4+ ; similar co-substitutions in synthetic cristobalite are known to modify the crystal structure, affecting the stability of the α and β forms and the observed transition between them. Here, for the first time, the dynamics and energy changes associated with the α-β phase transition in volcanic cristobalite are investigated using X-ray powder diffraction with simultaneous in situ heating and differential scanning calorimetry. At ambient temperature, volcanic cristobalite exists in the α form and has a larger cell volume than synthetic α-cristobalite; as a result, its diffraction pattern sits between ICDD α- and β-cristobalite library patterns, which could cause ambiguity in phase identification. On heating from ambient temperature, volcanic cristobalite exhibits a lower degree of thermal expansion than synthetic cristobalite, and it also has a lower α-β transition temperature (∼473 K) compared with synthetic cristobalite (upwards of 543 K); these observations are discussed in relation to the presence of Al 3+ and Na + defects. The transition shows a stable and reproducible hysteresis loop with α and β phases coexisting through the transition, suggesting that discrete crystals in the sample have different transition temperatures.

Carrier and polarization dynamics in monolayer MoS2: temperature and power dependence

NASA Astrophysics Data System (ADS)

Urbaszek, Bernhard; Lagarde, D.; Bouet, L.; Amand, T.; Marie, X.; Zhu, C. R.; Liu, B. L.; Tan, P. H.

2014-03-01

In monolayer (ML) MoS2 optical transitions across the direct bandgap are governed by chiral selection rules, allowing optical k-valley initialization. Here we present the first time resolved photoluminescence (PL) polarization measurements in MoS2 MLs, providing vital information on the electron valley dynamics. Using quasi-resonant excitation of the A-exciton transitions, we can infer that the PL decays within τ ~= 4ps. The PL polarization of Pc ~ 60 % remains nearly constant in time for experiments from 4K - 300K, a necessary condition for the success of future Valley Hall experiments. τ does not vary significantly over this temperature range. This is surprising when considering the decrease of Pc in continuous wave experiments when going from 4K to 300K reported in the literature. By tuning the laser following the shift of the A-exciton resonance with temperature we are able to recover at 300K ~ 80 % of the polarization observed at 4K. For pulsed laser excitation, we observe a decrease of Pc with increasing laser power at all temperatures.

Electron and lattice dynamics of transition metal thin films observed by ultrafast electron diffraction and transient optical measurements.

PubMed

Nakamura, A; Shimojima, T; Nakano, M; Iwasa, Y; Ishizaka, K

2016-11-01

We report the ultrafast dynamics of electrons and lattice in transition metal thin films (Au, Cu, and Mo) investigated by a combination of ultrafast electron diffraction (UED) and pump-probe optical methods. For a single-crystalline Au thin film, we observe the suppression of the diffraction intensity occuring in 10 ps, which direcly reflects the lattice thermalization via the electron-phonon interaction. By using the two-temperature model, the electron-phonon coupling constant ( g ) and the electron and lattice temperatures ( T e , T l ) are evaluated from UED, with which we simulate the transient optical transmittance. The simulation well agrees with the experimentally obtained transmittance data, except for the slight deviations at the initial photoexcitation and the relaxed quasi-equilibrium state. We also present the results similarly obtained for polycrystalline Au, Cu, and Mo thin films and demonstrate the electron and lattice dynamics occurring in metals with different electron-phonon coupling strengths.

Underlying mechanisms leading to El Niño-to-La Niña transition are unchanged under global warming

NASA Astrophysics Data System (ADS)

Yun, Kyung-Sook; Yeh, Sang-Wook; Ha, Kyung-Ja

2018-05-01

El Niño's transitions play critical roles in modulating severe weather and climate events. Therefore, understanding the dynamic factors leading to El Niño's transitions and its future projection is a great challenge in predicting the diverse socioeconomic influences of El Niño over the globe. This study focuses on two dynamic factors controlling the El Niño-to-La Niña transition from the present climate and to future climate, using the observation, the historical and the RCP8.5 simulations of Coupled Model Intercomparison phase 5 climate models. The first is the inter-basin coupling between the Indian Ocean and the western North Pacific through the subtropical high variability. The second is the enhanced sensitivity between sea surface temperature and a deep tropical convection in the central tropical Pacific during the El Niño's developing phase. We show that the dynamic factors leading to El Niño-to-La Niña transition in the present climate are unchanged in spite of the increase of greenhouse gas concentrations. We argue that the two dynamic factors are strongly constrained by the climatological precipitation distribution over the central tropical Pacific and western North Pacific as little changed from the present climate to future climate. This implies that two dynamical processes leading to El Niño-to-La Niña transitions in the present climate will also play a robust role in global warming.

Diffusive dynamics during the high-to-low density transition in amorphous ice

DOE PAGES

Perakis, Fivos; Amann-Winkel, Katrin; Lehmkuhler, Felix; ...

2017-06-26

Water exists in high- and low-density amorphous ice forms (HDA and LDA), which could correspond to the glassy states of high- (HDL) and low-density liquid (LDL) in the metastable part of the phase diagram. However, the nature of both the glass transition and the high-to-low-density transition are debated and new experimental evidence is needed. Here we combine wide-angle X-ray scattering (WAXS) with X-ray photon-correlation spectroscopy (XPCS) in the small-angle X-ray scattering (SAXS) geometry to probe both the structural and dynamical properties during the high-to-low-density transition in amorphous ice at 1 bar. By analyzing the structure factor and the radial distributionmore » function, the coexistence of two structurally distinct domains is observed at T = 125 K. XPCS probes the dynamics in momentum space, which in the SAXS geometry reflects structural relaxation on the nanometer length scale. The dynamics of HDA are characterized by a slow component with a large time constant, arising from viscoelastic relaxation and stress release from nanometer-sized heterogeneities. Above 110 K a faster, strongly temperature-dependent component appears, with momentum transfer dependence pointing toward nanoscale diffusion. This dynamical component slows down after transition into the low-density form at 130 K, but remains diffusive. In conclusion, the diffusive character of both the high- and low-density forms is discussed among different interpretations and the results are most consistent with the hypothesis of a liquid–liquid transition in the ultraviscous regime.« less

Diffusive dynamics during the high-to-low density transition in amorphous ice

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perakis, Fivos; Amann-Winkel, Katrin; Lehmkuhler, Felix

Water exists in high- and low-density amorphous ice forms (HDA and LDA), which could correspond to the glassy states of high- (HDL) and low-density liquid (LDL) in the metastable part of the phase diagram. However, the nature of both the glass transition and the high-to-low-density transition are debated and new experimental evidence is needed. Here we combine wide-angle X-ray scattering (WAXS) with X-ray photon-correlation spectroscopy (XPCS) in the small-angle X-ray scattering (SAXS) geometry to probe both the structural and dynamical properties during the high-to-low-density transition in amorphous ice at 1 bar. By analyzing the structure factor and the radial distributionmore » function, the coexistence of two structurally distinct domains is observed at T = 125 K. XPCS probes the dynamics in momentum space, which in the SAXS geometry reflects structural relaxation on the nanometer length scale. The dynamics of HDA are characterized by a slow component with a large time constant, arising from viscoelastic relaxation and stress release from nanometer-sized heterogeneities. Above 110 K a faster, strongly temperature-dependent component appears, with momentum transfer dependence pointing toward nanoscale diffusion. This dynamical component slows down after transition into the low-density form at 130 K, but remains diffusive. In conclusion, the diffusive character of both the high- and low-density forms is discussed among different interpretations and the results are most consistent with the hypothesis of a liquid–liquid transition in the ultraviscous regime.« less

Diffusive dynamics during the high-to-low density transition in amorphous ice

NASA Astrophysics Data System (ADS)

Perakis, Fivos; Amann-Winkel, Katrin; Lehmkühler, Felix; Sprung, Michael; Mariedahl, Daniel; Sellberg, Jonas A.; Pathak, Harshad; Späh, Alexander; Cavalca, Filippo; Schlesinger, Daniel; Ricci, Alessandro; Jain, Avni; Massani, Bernhard; Aubree, Flora; Benmore, Chris J.; Loerting, Thomas; Grübel, Gerhard; Pettersson, Lars G. M.; Nilsson, Anders

2017-08-01

Water exists in high- and low-density amorphous ice forms (HDA and LDA), which could correspond to the glassy states of high- (HDL) and low-density liquid (LDL) in the metastable part of the phase diagram. However, the nature of both the glass transition and the high-to-low-density transition are debated and new experimental evidence is needed. Here we combine wide-angle X-ray scattering (WAXS) with X-ray photon-correlation spectroscopy (XPCS) in the small-angle X-ray scattering (SAXS) geometry to probe both the structural and dynamical properties during the high-to-low-density transition in amorphous ice at 1 bar. By analyzing the structure factor and the radial distribution function, the coexistence of two structurally distinct domains is observed at T = 125 K. XPCS probes the dynamics in momentum space, which in the SAXS geometry reflects structural relaxation on the nanometer length scale. The dynamics of HDA are characterized by a slow component with a large time constant, arising from viscoelastic relaxation and stress release from nanometer-sized heterogeneities. Above 110 K a faster, strongly temperature-dependent component appears, with momentum transfer dependence pointing toward nanoscale diffusion. This dynamical component slows down after transition into the low-density form at 130 K, but remains diffusive. The diffusive character of both the high- and low-density forms is discussed among different interpretations and the results are most consistent with the hypothesis of a liquid-liquid transition in the ultraviscous regime.

Thermodynamics and Dynamics of Bose condensation in a quasi-homogeneous gas

NASA Astrophysics Data System (ADS)

Navon, Nir; Schmidutz, Tobias; Gotlibovych, Igor; Gaunt, Alexander; Robert-de-Saint-Vincent, Martin; Smith, Robert; Hadzibabic, Zoran

2014-05-01

We present an experimental study of the thermodynamics and dynamics of Bose-Einstein condensation (BEC) in an optical-box trap. We first characterize the critical point for BEC, and observe saturation of the thermal component in a partially condensed cloud, in agreement with Einstein's textbook picture of a purely statistical phase transition. We also observed the quantum Joule-Thomson effect, namely isoenthalpic cooling of a non-interacting gas. We then investigate the dynamics of Bose condensation in the box potential following a rapid temperature quench through the phase transition, and focus on the time-evolution of the condensed fraction, the coherence length and the mean-field shift, that we probe via Bragg spectroscopy.

Effects of Composite Pions on the Chiral Condensate within the PNJL Model at Finite Temperature

NASA Astrophysics Data System (ADS)

Blaschke, D.; Dubinin, A.; Ebert, D.; Friesen, A. V.

2018-05-01

We investigate the effect of composite pions on the behaviour of the chiral condensate at finite temperature within the Polyakov-loop improved NJL model. To this end we treat quark-antiquark correlations in the pion channel (bound states and scattering continuum) within a Beth-Uhlenbeck approach that uses medium-dependent phase shifts. A striking medium effect is the Mott transition which occurs when the binding energy vanishes and the discrete pion bound state merges the continuum. This transition is triggered by the lowering of the continuum edge due to the chiral restoration transition. This in turn also entails a modification of the Polyakov-loop so that the SU(3) center symmetry gets broken at finite temperature and dynamical quarks (and gluons) appear in the system, taking over the role of the dominant degrees of freedom from the pions. At low temperatures our model reproduces the chiral perturbation theory result for the chiral condensate while at high temperatures the PNJL model result is recovered. The new aspect of the current work is a consistent treatment of the chiral restoration transition region within the Beth-Uhlenbeck approach on the basis of mesonic phase shifts for the treatment of the correlations.

Disruption of Hydrogen-Bonding Network Eliminates Water Anomalies Normally Observed on Cooling to Its Calorimetric Glass Transition

DOE PAGES

Borreguero, Jose M.; Mamontov, Eugene

2017-04-11

Here, the calorimetric glass-transition temperature of water is 136 K, but extrapolation of thermodynamic and relaxation properties of water from ambient temperature to below its homogeneous nucleation temperature T H = 235 K predicts divergence at T S = 228 K. The “no-man’s land” between the T H and glassy water crystallization temperature of 150 K, which is encountered on warming up from the vitrified state, precludes a straightforward reconciliation of the two incompatible temperature dependences of water properties, above 235 K and below 150 K. The addition of lithium chloride to water allows bypassing both T H and Tmore » S on cooling, resulting in the dynamics with no features except the calorimetric glass transition, still at 136 K. We show that lithium chloride prevents hydrogen-bonding network completion in water on cooling, as manifested, in particular, in changing microscopic diffusion mechanism of the water molecules. Thus thermodynamic and relaxation peculiarities exhibited by pure water on cooling to its glass transition, such as the existence of the T H and T S, must be associated specifically with the hydrogen-bonding network.« less

An Nmr Study of Supercooled Water Under Nanoconfinement by Hydrophobic Surfaces

NASA Astrophysics Data System (ADS)

Ling, Yan-Chun

The main focus of this dissertation is studying the properties of bulk water, confined water, and interfacial water. The thermodynamics, dynamics and state of water are investigated by DSC and 1H NMR methods. Hydrophobic slit-shaped pores with tunable pore size from 0.5 nm to 1.6 nm are applied as confinement media in our experiments. By confining water in nanopores, we are able to cool the water lower than its homogeneous nucleation temperature 235 K at ambient pressure and access the "no man's land". Both experimental and simulation results show water has heterogeneity property, with two "phases", one is high-density liquid (HDL) "phase" which has dense-packing structure, the other is low-density liquid (LDL) "phase" which has more tetrahedral structure. At room temperature, HDL and LDL two "phases" can coexist in millisecond time scale and 10 nanometer length scale. The room temperature water structure is dominated by HDL structure. By decreasing the temperature, HDL could convert to LDL gradually. At 200 K, LDL dominates the liquid state of water. It is of importance to emphasis, for water confined in nanopores there is no crystallization above 200 K. A dynamic crossover at 225 K in the liquid state is observed in our hydrophobic system, similar to that observed in hydrophilic system. This proves such dynamic crossover is not induced by crystallization or surface effect, but originally from the intrinsic properties of water. At 190 K, we find a second change of rotational correlation time, which resembles the glassification process of supercooled confined water, suggesting a higher rotational glass transition temperature for bulk water. In the lower temperature range 145 K water. In the lower temperature range 145 K < T < 165 K, the interfacial water induced glass transition is observed. At sufficient low temperature, confinement plays an important role for the induced glass transition. We also study the properties of interfacial water by confining water in smaller hydrophobic pores. It shows the interfacial water remains liquid state at 140 K. There is an Arrhenius to Arrhenius dynamic crossover at 170 K due to the rotational motion slowing down. Comparing to bulk water, interfacial water has fast rotation but effectively immobile. Our studies thus provide a complete picture for the rather controversial supercooled region and also differentiate the properties of bulk water, confined water and interfacial water using different techniques.

Vulcanization characteristics and dynamic mechanical behavior of natural rubber reinforced with silane modified silica.

PubMed

Chonkaew, Wunpen; Minghvanish, Withawat; Kungliean, Ulchulee; Rochanawipart, Nutthaya; Brostow, Witold

2011-03-01

Two silane coupling agents were used for hydrolysis-condensation reaction modification of nanosilica surfaces. The surface characteristics were analyzed using Fourier transform infrared spectroscopy (FTIR). The vulcanization kinetics of natural rubber (NR) + silica composites was studied and compared to behavior of the neat NR using differential scanning calorimetry (DSC) in the dynamic scan mode. Dynamic mechanical analysis (DMA) was performed to evaluate the effects of the surface modification. Activation energy E(a) values for the reaction are obtained. The presence of silica, modified or otherwise, inhibits the vulcanization reaction of NR. The neat silica containing system has the lowest cure rate index and the highest activation energy for the vulcanization reaction. The coupling agent with longer chains causes more swelling and moves the glass transition temperature T(g) downwards. Below the glass transition region, silica causes a lowering of the dynamic storage modulus G', a result of hindering the cure reaction. Above the glass transition, silica-again modified or otherwise-provides the expected reinforcement effect.

Tensile Strength of Carbon Nanotubes Under Realistic Temperature and Strain Rate

NASA Technical Reports Server (NTRS)

Wei, Chen-Yu; Cho, Kyeong-Jae; Srivastava, Deepak; Biegel, Bryan (Technical Monitor)

2002-01-01

Strain rate and temperature dependence of the tensile strength of single-wall carbon nanotubes has been investigated with molecular dynamics simulations. The tensile failure or yield strain is found to be strongly dependent on the temperature and strain rate. A transition state theory based predictive model is developed for the tensile failure of nanotubes. Based on the parameters fitted from high-strain rate and temperature dependent molecular dynamics simulations, the model predicts that a defect free micrometer long single-wall nanotube at 300 K, stretched with a strain rate of 1%/hour, fails at about 9 plus or minus 1% tensile strain. This is in good agreement with recent experimental findings.

Seasonal photosynthetic activity in evergreen conifer leaves monitored with spectral reflectance

NASA Astrophysics Data System (ADS)

Wong, C. Y.; Gamon, J. A.

2013-12-01

Boreal evergreen conifers must maintain photosynthetic systems in environments where temperatures vary greatly across seasons from high temperatures in the summer to freezing levels in the winter. This involves seasonal downregulation and photoprotection during periods of extreme temperatures. To better understand this downregulation, seasonal dynamics of photosynthesis of lodgepole (Pinus contorta D.) and ponderosa pine (Pinus ponderosa D.) were monitored in Edmonton, Canada over two years. Spectral reflectance at the leaf and stand scales was measured weekly and the Photochemical Reflectance Index (PRI), often used as a proxy for chlorophyll and carotenoid pigment levels and photosynthetic light-use efficiency (LUE), was used to track the seasonal dynamics of photosynthetic activity. Additional physiological measurements included leaf pigment content, chlorophyll fluorescence, and gas exchange. All the metrics indicate large seasonal changes in photosynthetic activity, with a sharp transition from winter downregulation to active photosynthesis in the spring and a more gradual fall transition into winter. The PRI was a good indicator of several other variables including seasonally changing photosynthetic activity, chlorophyll fluorescence, photosynthetic LUE, and pigment pool sizes. Over the two-year cycle, PRI was primarily driven by changes in constitutive (chlorophyll:carotenoid) pigment levels correlated with seasonal photosynthetic activity, with a much smaller variation caused by diurnal changes in xanthophyll cycle activity (conversion between violaxanthin & zeaxanthin). Leaf and canopy scale PRI measurements exhibited parallel responses during the winter-spring transition. Together, our findings indicate that evergreen conifers photosynthetic system possesses a remarkable degree of resilience in response to large temperature changes across seasons, and that optical remote sensing can be used to observe the seasonal effects on photosynthesis and productivity. Furthermore, the seasonal transitions between photosynthetically active and inactive states can be clearly detected by the PRI. These findings have implications for using remote sensing to detect dynamics in photosynthetic activity in response to changing growing season length in northern latitudes.

Disorder-induced amorphization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lam, N.Q.; Okamoto, P.R.; Li, Mo

1997-03-01

Many crystalline materials undergo a crystalline-to-amorphous (c-a) phase transition when subjected to energetic particle irradiation at low temperatures. By focusing on the mean-square static atomic displacement as a generic measure of chemical and topological disorder, we are led quite naturally to a generalized version of the Lindemann melting criterion as a conceptual framework for a unified thermodynamic approach to solid-state amorphizing transformations. In its simplest form, the generalized Lindemann criterion assumes that the sum of the static and dynamic mean-square atomic displacements is constant along the polymorphous melting curve so that c-a transformations can be understood simply as melting ofmore » a critically-disordered crystal at temperatures below the glass transition temperature where the supercooled liquid can persist indefinitely in a configurationally-frozen state. Evidence in support of the generalized Lindemann melting criterion for amorphization is provided by a large variety of experimental observations and by molecular dynamics simulations of heat-induced melting and of defect-induced amorphization of intermetallic compounds.« less

Coherent generation of symmetry-forbidden phonons by light-induced electron-phonon interactions in magnetite

NASA Astrophysics Data System (ADS)

Borroni, S.; Baldini, E.; Katukuri, V. M.; Mann, A.; Parlinski, K.; Legut, D.; Arrell, C.; van Mourik, F.; Teyssier, J.; Kozlowski, A.; Piekarz, P.; Yazyev, O. V.; Oleś, A. M.; Lorenzana, J.; Carbone, F.

2017-09-01

Symmetry breaking across phase transitions often causes changes in selection rules and emergence of optical modes which can be detected via spectroscopic techniques or generated coherently in pump-probe experiments. In second-order or weakly first-order transitions, fluctuations of the ordering field are present above the ordering temperature, giving rise to intriguing precursor phenomena, such as critical opalescence. Here, we demonstrate that in magnetite (Fe3O4 ) light excitation couples to the critical fluctuations of the charge order and coherently generates structural modes of the ordered phase above the critical temperature of the Verwey transition. Our findings are obtained by detecting coherent oscillations of the optical constants through ultrafast broadband spectroscopy and analyzing their dependence on temperature. To unveil the coupling between the structural modes and the electronic excitations, at the origin of the Verwey transition, we combine our results from pump-probe experiments with spontaneous Raman scattering data and theoretical calculations of both the phonon dispersion curves and the optical constants. Our methodology represents an effective tool to study the real-time dynamics of critical fluctuations across phase transitions.

Glasslike dynamical behavior of the plastocyanin hydration water

NASA Astrophysics Data System (ADS)

Bizzarri, Anna Rita; Paciaroni, Alessandro; Cannistraro, Salvatore

2000-09-01

The dynamical behavior of water around plastocyanin has been investigated in a wide temperature range by molecular dynamics simulation. The mean square displacements of water oxygen atoms show, at long times, a tα trend for all temperatures. Below 150 K, α is constant and equal to 1; at higher temperatures it drops to a value significantly smaller than 1, and thereafter decreases with increasing temperature. The occurrence of such an anomalous diffusion matches the onset of the dynamical transition observed in the protein. The intermediate scattering function of water is characterized, at high temperature, by a stretched exponential decay evolving, at low temperature, toward a two step relaxation behavior, which becomes more evident on increasing the exchanged wave vector q. Both the mean square displacements and the intermediate scattering functions show, beyond the ballistic regime, a plateau, which progressively extends for longer times as long as the temperature is lowered, such behavior reflecting trapping of water molecules within a cage formed by the nearest neighbors. At low temperature, a low frequency broad inelastic peak is observed in the dynamical structure factor of hydration water; such an excess of vibrational modes being reminiscent of the boson peak, characteristic of disordered, amorphous systems. All these features, which are typical of complex systems, can be traced back to the glassy character of the hydration water and suggest a dynamical coupling occurring at the macromolecule-solvent interface.

Trp zipper folding kinetics by molecular dynamics and temperature-jump spectroscopy

PubMed Central

Snow, Christopher D.; Qiu, Linlin; Du, Deguo; Gai, Feng; Hagen, Stephen J.; Pande, Vijay S.

2004-01-01

We studied the microsecond folding dynamics of three β hairpins (Trp zippers 1–3, TZ1–TZ3) by using temperature-jump fluorescence and atomistic molecular dynamics in implicit solvent. In addition, we studied TZ2 by using time-resolved IR spectroscopy. By using distributed computing, we obtained an aggregate simulation time of 22 ms. The simulations included 150, 212, and 48 folding events at room temperature for TZ1, TZ2, and TZ3, respectively. The all-atom optimized potentials for liquid simulations (OPLSaa) potential set predicted TZ1 and TZ2 properties well; the estimated folding rates agreed with the experimentally determined folding rates and native conformations were the global potential-energy minimum. The simulations also predicted reasonable unfolding activation enthalpies. This work, directly comparing large simulated folding ensembles with multiple spectroscopic probes, revealed both the surprising predictive ability of current models as well as their shortcomings. Specifically, for TZ1–TZ3, OPLS for united atom models had a nonnative free-energy minimum, and the folding rate for OPLSaa TZ3 was sensitive to the initial conformation. Finally, we characterized the transition state; all TZs fold by means of similar, native-like transition-state conformations. PMID:15020773

Trp zipper folding kinetics by molecular dynamics and temperature-jump spectroscopy

NASA Astrophysics Data System (ADS)

Snow, Christopher D.; Qiu, Linlin; Du, Deguo; Gai, Feng; Hagen, Stephen J.; Pande, Vijay S.

2004-03-01

We studied the microsecond folding dynamics of three hairpins (Trp zippers 1-3, TZ1-TZ3) by using temperature-jump fluorescence and atomistic molecular dynamics in implicit solvent. In addition, we studied TZ2 by using time-resolved IR spectroscopy. By using distributed computing, we obtained an aggregate simulation time of 22 ms. The simulations included 150, 212, and 48 folding events at room temperature for TZ1, TZ2, and TZ3, respectively. The all-atom optimized potentials for liquid simulations (OPLSaa) potential set predicted TZ1 and TZ2 properties well; the estimated folding rates agreed with the experimentally determined folding rates and native conformations were the global potential-energy minimum. The simulations also predicted reasonable unfolding activation enthalpies. This work, directly comparing large simulated folding ensembles with multiple spectroscopic probes, revealed both the surprising predictive ability of current models as well as their shortcomings. Specifically, for TZ1-TZ3, OPLS for united atom models had a nonnative free-energy minimum, and the folding rate for OPLSaa TZ3 was sensitive to the initial conformation. Finally, we characterized the transition state; all TZs fold by means of similar, native-like transition-state conformations.

CDW fluctuations and the pseudogap in the single-particle conductivity of quasi-1D Peierls CDW systems: II.

PubMed

Kupčić, I; Rukelj, Z; Barišić, S

2014-05-14

The current-dipole Kubo formula for the dynamical conductivity of interacting multiband electronic systems derived in Kupčić et al (2013 J. Phys.: Condens. Matter 25 145602) is illustrated on the Peierls model for quasi-one-dimensional systems with the charge-density-wave (CDW) instability. Using the microscopic representation of the Peierls model, it is shown in which way the scattering of conduction electrons by CDW fluctuations affects the dynamical conductivity at temperatures above and well below the CDW transition temperature. The generalized Drude formula for the intraband conductivity is derived in the ordered CDW state well below the transition temperature. The natural extension of this formula to the case where the intraband memory function is dependent on frequency and wave vectors is also presented. It is shown that the main adventage of such a memory-function conductivity model is that it can be easily extended to study the dynamical conductivity and the electronic Raman scattering in more complicated multiband electronic systems in a way consistent with the law of conservation of energy. The incoherent interband conductivity in the CDW pseudogap state is briefly discussed as well.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cadiz, Fabian, E-mail: cadiz@insa-toulouse.fr; Tricard, Simon; Gay, Maxime

Developments in optoelectronics and spin-optronics based on transition metal dichalcogenide monolayers (MLs) need materials with efficient optical emission and well-defined transition energies. In as-exfoliated MoS{sub 2} MLs, the photoluminescence (PL) spectra even at low temperature consist typically of broad, overlapping contributions from neutral, charged excitons (trions) and localized states. Here, we show that in superacid treated MoS{sub 2} MLs, the PL intensity increases by up to 60 times at room temperature. The neutral and charged exciton transitions are spectrally well separated in PL and reflectivity at T = 4 K, with linewidth for the neutral exciton of 15 meV, but both transitions have similarmore » intensities compared to the ones in as-exfoliated MLs at the same temperature. Time resolved experiments uncover picoseconds recombination dynamics analyzed separately for charged and neutral exciton emissions. Using the chiral interband selection rules, we demonstrate optically induced valley polarization for both complexes and valley coherence for only the neutral exciton.« less

Vortex dynamics in superconducting transition edge sensors

NASA Astrophysics Data System (ADS)

Ezaki, S.; Maehata, K.; Iyomoto, N.; Asano, T.; Shinozaki, B.

2018-02-01

The temperature dependence of the electrical resistance (R-T) and the current-voltage (I-V) characteristics has been measured and analyzed in a 40 nm thick Ti thin film, which is used as a transition edge sensor (TES). The analyses of the I-V characteristics with the vortex-antivortex pair dissociation model indicate the possible existence of the Berezinskii-Kosterlitz-Thouless (BKT) transition in two-dimensional superconducting Ti thin films. We investigated the noise due to the vortices' flow in TESs. The values of the current noise spectral density in the TESs were estimated by employing the vortex dynamics caused by the BKT transition in the Ti thin films. The estimated values of the current noise spectral density induced by the vortices' flow were in respectable agreement with the values of excess noise experimentally observed in the TESs with Ti/Au bilayer.

Kinetics of a bioactive compound (caffeine) mobility at the vicinity of the mechanical glass transition temperature induced by gelling polysaccharide.

PubMed

Jiang, Bin; Kasapis, Stefan

2011-11-09

An investigation of the diffusional mobility of a bioactive compound (caffeine) within the high-solid (80.0% w/w) matrices of glucose syrup and κ-carrageenan plus glucose syrup exhibiting distinct mechanical glass transition properties is reported. The experimental temperature range was from 20 to -60 °C, and the techniques of modulated differential scanning calorimetry, small deformation dynamic oscillation in shear, and UV spectrometry were employed. Calorimetric and mechanical measurements were complementary in recording the relaxation dynamics of high-solid matrices upon controlled heating. Predictions of the reaction rate theory and the combined WLF/free volume framework were further utilized to pinpoint the glass transition temperature (T(g)) of the two matrices in the softening dispersion. Independent of composition, calorimetry yielded similar T(g) predictions for both matrices at this level of solids. Mechanical experimentation, however, was able to detect the effect of adding gelling polysaccharide to glucose syrup as an accelerated pattern of vitrification leading to a higher value of T(g). Kinetic rates of caffeine diffusion within the experimental temperature range were taken with UV spectroscopy. These demonstrated the pronounced effect of the gelling κ-carrageenan/glucose syrup mixture to retard diffusion of the bioactive compound near the mechanical T(g). Modeling of the diffusional mobility of caffeine produced activation energy and fractional free-volume estimates, which were distinct from those of the carbohydrate matrix within the glass transition region. This result emphasizes the importance of molecular interactions between macromolecular matrix and small bioactive compound in glass-related relaxation phenomena.

Taking Ockham's razor to enzyme dynamics and catalysis.

PubMed

Glowacki, David R; Harvey, Jeremy N; Mulholland, Adrian J

2012-01-29

The role of protein dynamics in enzyme catalysis is a matter of intense current debate. Enzyme-catalysed reactions that involve significant quantum tunnelling can give rise to experimental kinetic isotope effects with complex temperature dependences, and it has been suggested that standard statistical rate theories, such as transition-state theory, are inadequate for their explanation. Here we introduce aspects of transition-state theory relevant to the study of enzyme reactivity, taking cues from chemical kinetics and dynamics studies of small molecules in the gas phase and in solution--where breakdowns of statistical theories have received significant attention and their origins are relatively better understood. We discuss recent theoretical approaches to understanding enzyme activity and then show how experimental observations for a number of enzymes may be reproduced using a transition-state-theory framework with physically reasonable parameters. Essential to this simple model is the inclusion of multiple conformations with different reactivity.

Mott-Hubbard transition and Anderson localization: A generalized dynamical mean-field theory approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuchinskii, E. Z.; Nekrasov, I. A.; Sadovskii, M. V.

The DOS, the dynamic (optical) conductivity, and the phase diagram of a strongly correlated and strongly disordered paramagnetic Anderson-Hubbard model are analyzed within the generalized dynamical mean field theory (DMFT + {sigma} approximation). Strong correlations are taken into account by the DMFT, and disorder is taken into account via an appropriate generalization of the self-consistent theory of localization. The DMFT effective single-impurity problem is solved by a numerical renormalization group (NRG); we consider the three-dimensional system with a semielliptic DOS. The correlated metal, Mott insulator, and correlated Anderson insulator phases are identified via the evolution of the DOS and dynamicmore » conductivity, demonstrating both the Mott-Hubbard and Anderson metal-insulator transition and allowing the construction of the complete zero-temperature phase diagram of the Anderson-Hubbard model. Rather unusual is the possibility of a disorder-induced Mott insulator-to-metal transition.« less

Prethermalization and persistent order in the absence of a thermal phase transition

NASA Astrophysics Data System (ADS)

Halimeh, Jad C.; Zauner-Stauber, Valentin; McCulloch, Ian P.; de Vega, Inés; Schollwöck, Ulrich; Kastner, Michael

2017-01-01

We numerically study the dynamics after a parameter quench in the one-dimensional transverse-field Ising model with long-range interactions (∝1 /rα with distance r ), for finite chains and also directly in the thermodynamic limit. In nonequilibrium, i.e., before the system settles into a thermal state, we find a long-lived regime that is characterized by a prethermal value of the magnetization, which in general differs from its thermal value. We find that the ferromagnetic phase is stabilized dynamically: as a function of the quench parameter, the prethermal magnetization shows a transition between a symmetry-broken and a symmetric phase, even for those values of α for which no finite-temperature transition occurs in equilibrium. The dynamical critical point is shifted with respect to the equilibrium one, and the shift is found to depend on α as well as on the quench parameters.

Dynamics of Phase Transitions in a Snow Mass Containing Water-Soluble Salt Particles

NASA Astrophysics Data System (ADS)

Zelenko, V. L.; Heifets, L. I.; Orlov, Yu. N.; Voskresenskiy, N. M.

2018-07-01

A macrokinetic approach is used to describe the dynamics of phase transitions in a snow mass containing water-soluble salt particles. Equations are derived that describe the rate of salt granule dissolution and the change in the phase composition and temperature of a snow mass under the conditions of heat transfer with an isothermal surface. An experimental setup that models the change in the state of a snow mass placed on an isothermal surface is created to verify theoretical conclusions. Experimental observations of the change in temperature of the snow mass are compared to theoretical calculations. The mathematical model that is developed can be used to predict the state of a snow mass on roads treated with a deicing agent, or to analyze the state of snow masses containing water-soluble salt inclusions and resting on mountain slopes.

The length and time scales of water's glass transitions

NASA Astrophysics Data System (ADS)

Limmer, David T.

2014-06-01

Using a general model for the equilibrium dynamics of supercooled liquids, I compute from molecular properties the emergent length and time scales that govern the nonequilibrium relaxation behavior of amorphous ice prepared by rapid cooling. Upon cooling, the liquid water falls out of equilibrium whereby the temperature dependence of its relaxation time is predicted to change from super-Arrhenius to Arrhenius. A consequence of this crossover is that the location of the apparent glass transition temperature depends logarithmically on cooling rate. Accompanying vitrification is the emergence of a dynamical length-scale, the size of which depends on the cooling rate and varies between angstroms and tens of nanometers. While this protocol dependence clarifies a number of previous experimental observations for amorphous ice, the arguments are general and can be extended to other glass forming liquids.

The length and time scales of water's glass transitions.

PubMed

Limmer, David T

2014-06-07

Using a general model for the equilibrium dynamics of supercooled liquids, I compute from molecular properties the emergent length and time scales that govern the nonequilibrium relaxation behavior of amorphous ice prepared by rapid cooling. Upon cooling, the liquid water falls out of equilibrium whereby the temperature dependence of its relaxation time is predicted to change from super-Arrhenius to Arrhenius. A consequence of this crossover is that the location of the apparent glass transition temperature depends logarithmically on cooling rate. Accompanying vitrification is the emergence of a dynamical length-scale, the size of which depends on the cooling rate and varies between angstroms and tens of nanometers. While this protocol dependence clarifies a number of previous experimental observations for amorphous ice, the arguments are general and can be extended to other glass forming liquids.

Motion control in free-standing shape-memory actuators

NASA Astrophysics Data System (ADS)

Belmonte, Alberto; Lama, Giuseppe C.; Cerruti, Pierfrancesco; Ambrogi, Veronica; Fernández-Francos, Xavier; De la Flor, Silvia

2018-07-01

In this work, free-standing shape-memory thermally triggered actuators are developed by laminating ‘thiol-epoxy’-based glassy thermoset (GT) and stretched liquid-crystalline network (LCN) films. A sequential curing process was used to obtain GTs with tailored thermomechanical properties and network relaxation dynamics, and also to assemble the final actuator. The actuation extent, rate and time were studied by varying the GT and the heating rate in thermo-actuation with an experimental approach. The results demonstrate that it is possible to tailor the actuation rate and time by designing GT materials with a glass transition temperature close to that of the liquid-crystalline-to-isotropic phase transition of the LCN, thus making it possible to couple the two processes. Such coupling is also possible in rapid heating processes even when the glass transition temperature of the GT is clearly lower than the isotropization temperature of the LCN, depending on the network relaxation dynamics of the GT and the presence of thermal gradients within the actuators. Interestingly, varying the GT network relaxation dynamics does not affect the actuation extent. As predicted by the analytical model developed in our previous work, the modulus of the GT layer is mainly responsible for the actuation extent. Finally, to demonstrate the enhanced control of the actuation, specifically designed actuators were assembled in a three-dimensional actuating device able to make complex motions (including ‘S-type’ bending). This approach makes it possible to engineer advanced functional materials for application in self-adaptable structures and soft robotics.

Irradiation embrittlement characterization of the EUROFER 97 material

NASA Astrophysics Data System (ADS)

Kytka, M.; Brumovsky, M.; Falcnik, M.

2011-02-01

The paper summarizes original results of irradiation embrittlement study of EUROFER 97 material that has been proposed as one candidate of structural materials for future fusion energy systems and GEN IV. Test specimens were manufactured from base metal as well as from weld metal and tested in initial unirradiated condition and also after neutron irradiation. Irradiation embrittlement was characterized by testing of toughness properties at transition temperature region - static fracture toughness and dynamic fracture toughness properties, all in sub-size three-point bend specimens (27 × 4 × 3 mm 3). Testing and evaluation was performed in accordance with ASTM and ESIS standards, fracture toughness KJC and KJd data were also evaluated with the "Master curve" approach. Moreover, J- R dependencies were determined and analyzed. The paper compares unirradiated and irradiated properties as well as changes in transition temperature shifts of these material parameters. Discussion about the correlation between static and dynamic properties is also given. Results from irradiation of EUROFER 97 show that this steel - base metal as well as weld metal - is suitable as a structural material for reactor pressure vessels of innovative nuclear systems - fusion energy systems and GEN IV. Transition temperature shifts after neutron irradiation by 2.5 dpa dose show a good agreement in the case of EUROFER 97 base material for both static and dynamic fracture toughness tests. From the results it can be concluded that there is a low sensitivity of weld metal to neutron irradiation embrittlement in comparison with EUROFER 97 base metal.

Thermal and athermal crackling noise in ferroelastic nanostructures.

PubMed

Zhao, Z; Ding, X; Sun, J; Salje, E K H

2014-04-09

The evolution of ferroelastic microstructures under external shear is determined by large-scale molecular dynamics simulations in two and three dimensions. Ferroelastic pattern formation was found to be almost identical in two and three dimensions, with only the ferroelastic transition temperature changing. The twin patterns generated by shear deformation depend strongly on temperature, with high wall densities nucleating under optimized temperature conditions. The dynamical tweed and mobile kink movement inside the twin walls is continuous and thermally activated at high temperatures, and becomes jerky and athermal at low temperatures. With decreasing temperature, the statistical distributions of dynamical tweed and kinks vary from a Vogel-Fulcher law P(E)~exp-(E/(T-TVF)) to an athermal power-law distribution P(E)~E-E. During the yield event, the nucleation of needles and kinks is always jerky, and the energy of the jerks is power-law distributed. Low-temperature yield proceeds via one large avalanche. With increasing temperature, the large avalanche is thermally broken up into a multitude of small segments. The power-law exponents reflect the changes in temperature, even in the athermal regime.

Nanoscopic dynamics of phospholipid in unilamellar vesicles: Effect of gel to fluid phase transition

DOE PAGES

Sharma, V. K.; Mamontov, E.; Anunciado, D. B.; ...

2015-03-04

Dynamics of phospholipids in unilamellar vesicles (ULV) is of interest in biology, medical, and food sciences since these molecules are widely used as biocompatible agents and a mimic of cell membrane systems. We have investigated the nanoscopic dynamics of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) phospholipid in ULV as a function of temperature using elastic and quasielastic neutron scattering (QENS). The dependence of the signal on the scattering momentum transfer, which is a critical advantage of neutron scattering techniques, allows the detailed analysis of the lipid motions that cannot be carried out by other means. In agreement with a differential scanning calorimetry measurement, amore » sharp rise in the elastic scattering intensity below ca. 296 K indicates a phase transition from the high-temperature fluid phase to the low-temperature solid gel phase. The microscopic lipid dynamics exhibits qualitative differences between the solid gel phase (in a measurement at 280 K) and the fluid phase (in a measurement at a physiological temperature of 310 K). The data analysis invariably shows the presence of two distinct motions: the whole lipid molecule motion within a monolayer, or lateral diffusion, and the relatively faster internal motion of the DMPC molecule. The lateral diffusion of the whole lipid molecule is found to be Fickian in character, whereas the internal lipid motions are of localized character, consistent with the structure of the vesicles. The lateral motion slows down by an order of magnitude in the solid gel phase, whereas for the internal motion not only the time scale, but also the character of the motion changes upon the phase transition. In the solid gel phase, the lipids are more ordered and undergo uniaxial rotational motion. However, in the fluid phase, the hydrogen atoms of the lipid tails undergo confined translation diffusion rather than uniaxial rotational diffusion. The localized translational diffusion of the hydrogen atoms of the lipid tails is a manifestation of the flexibility of the chains acquired in the fluid phase. Because of this flexibility, both the local diffusivity and the confinement volume for the hydrogen atoms increase linearly from near the lipid s polar head group to the end of its hydrophobic tail. Our results present a quantitative and detailed picture of the effect of the gel-fluid phase transition on the nanoscopic lipid dynamics in ULV. Lastly, the data analysis approach developed here has a potential for probing the dynamic response of lipids to the presence of additional cell membrane components.« less

Electronic excitation induced amorphization in titanate pyrochlores: an ab initio molecular dynamics study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiao, Haiyan Y.; Weber, William J.; Zhang, Yanwen

2015-02-09

In this study, the response of titanate pyrochlores (A 2Ti 2O 7, A = Y, Gd and Sm) to electronic excitation is investigated utilizing an ab initio molecular dynamics method. All the titanate pyrochlores are found to undergo a crystalline-to-amorphous structural transition under a low concentration of electronic excitations. The transition temperature at which structural amorphization starts to occur depends on the concentration of electronic excitations. During the structural transition, O 2-like molecules are formed, and this anion disorder further drives cation disorder that leads to an amorphous state. This study provides new insights into the mechanisms of amorphization inmore » titanate pyrochlores under laser, electron and ion irradiations.« less

Thermal stress modification in regenerated fiber Bragg grating via manipulation of glass transition temperature based on CO₂-laser annealing.

PubMed

Lai, Man-Hong; Lim, Kok-Sing; Gunawardena, Dinusha S; Yang, Hang-Zhou; Chong, Wu-Yi; Ahmad, Harith

2015-03-01

In this work, we have demonstrated thermal stress relaxation in regenerated fiber Bragg gratings (RFBGs) by using direct CO₂-laser annealing technique. After the isothermal annealing and slow cooling process, the Bragg wavelength of the RFBG has been red-shifted. This modification is reversible by re-annealing and rapid cooling. It is repeatable with different cooling process in the subsequent annealing treatments. This phenomenon can be attributed to the thermal stress modification in the fiber core by means of manipulation of glass transition temperature with different cooling rates. This finding in this investigation is important for accurate temperature measurement of RFBG in dynamic environment.

Two-photon excitation of nitric oxide fluorescence as a temperature indicator in unsteady gas-dynamic processes

NASA Technical Reports Server (NTRS)

Mckenzie, R. L.; Gross, K. P.

1980-01-01

A laser induced fluorescence technique, suitable for measuring fluctuating temperatures in cold turbulent flows containing very low concentrations of nitric oxide is described. Temperatures below 300 K may be resolved with signal to noise ratios greater than 50 to 1 using high peak power, tunable dye lasers. The method relies on the two photon excitation of selected ro-vibronic transitions. The analysis includes the effects of fluorescence quenching and shows the technique to be effective at all densities below ambient. Signal to noise ratio estimates are based on a preliminary measurement of the two photon absorptivity for a selected rotational transition in the NO gamma (0,0) band.

A muon spin relaxation study of the metal-organic magnet Ni(TCNQ)2

NASA Astrophysics Data System (ADS)

Berlie, Adam; Terry, Ian; Giblin, Sean; Lancaster, Tom; Szablewski, Marek

2013-05-01

An investigation of the magnetism of the deuterated form of the metal-organic ferromagnet Ni(TCNQ)2 using the muon spin relaxation technique, is reported. Ni(TCNQ-D4)2 was synthesized in a similar manner to the protio-form, and the crystalline product formed was found to have a Curie temperature of TC=20 K. This transition temperature was 18% larger than that of the protio-form synthesized in our laboratory. Muon spin relaxation measurements were performed in Zero Field (ZF) and in Longitudinal Fields (LF) of up to 0.45 T. The ZF data confirmed that the sample undergoes a bulk ferromagnetic transition at a temperature similar to that observed by the bulk magnetization data. However, ZF measurements also showed that another transition occurs below approximately 6 K, which is believed to be a transition to a magnetic glassy state. The LF results indicate that a significant dynamical component to the magnetism is present below TC as LF fields up to 0.45 T cannot completely re-polarise the spins of the implanted muons. Moreover, at 5 mT, the data can be fit using a damped oscillatory function. Taken together, the ZF and LF results suggest the presence of two dominant sites for implanted muons, one of which is strongly coupled to the bulk magnetic transition and the other that is more weakly coupled and has a dynamical magnetic environment below TC. Such a situation may be a consequence of muon spin relaxation probing core and surface magnetic environments of nanoparticles or clusters.

Traversing the folding pathway of proteins using temperature-aided cascade molecular dynamics with conformation-dependent charges.

PubMed

Jani, Vinod; Sonavane, Uddhavesh; Joshi, Rajendra

2016-07-01

Protein folding is a multi-micro second time scale event and involves many conformational transitions. Crucial conformational transitions responsible for biological functions of biomolecules are difficult to capture using current state-of-the-art molecular dynamics (MD) simulations. Protein folding, being a stochastic process, witnesses these transitions as rare events. Many new methodologies have been proposed for observing these rare events. In this work, a temperature-aided cascade MD is proposed as a technique for studying the conformational transitions. Folding studies for Engrailed homeodomain and Immunoglobulin domain B of protein A have been carried out. Using this methodology, the unfolded structures with RMSD of 20 Å were folded to a structure with RMSD of 2 Å. Three sets of cascade MD runs were carried out using implicit solvation, explicit solvation, and charge updation scheme. In the charge updation scheme, charges based on the conformation obtained are calculated and are updated in the topology file. In all the simulations, the structure of 2 Å was reached within a few nanoseconds using these methods. Umbrella sampling has been performed using snapshots from the temperature-aided cascade MD simulation trajectory to build an entire conformational transition pathway. The advantage of the method is that the possible pathways for a particular reaction can be explored within a short duration of simulation time and the disadvantage is that the knowledge of the start and end state is required. The charge updation scheme adds the polarization effects in the force fields. This improves the electrostatic interaction among the atoms, which may help the protein to fold faster.

Noise Spectroscopy in Strongly Correlated Oxides

NASA Astrophysics Data System (ADS)

Alsaqqa, Ali M.

Strongly correlated materials are an interesting class of materials, thanks to the novel electronic and magnetic phenomena they exhibit as a result of the interplay of various degrees of freedom. This gives rise to an array of potential applications, from Mott-FET to magnetic storage. Many experimental probes have been used to study phase transitions in strongly correlated oxides. Among these, resistance noise spectroscopy, together with conventional transport measurements, provides a unique viewpoint to understand the microscopic dynamics near the phase transitions in these oxides. In this thesis, utilizing noise spectroscopy and transport measurements, four different strongly correlated materials were studied: (1) neodymium nickel oxide (NdNiO 3) ultrathin films, (2) vanadium dioxide (VO2) microribbons, (3) copper vanadium bronze (CuxV2O 5) microribbons and (4) niobium triselenide (NbSe3) microribbons. Ultra thin films of rare-earth nickelates exhibit several temperature-driven phase transitions. In this thesis, we studied the metal-insulator and Neel transitions in a series of NdNiO3 films with different lattice mismatches. Upon colling down, the metal-insulator phase transition is accompanied by a structural (orthorohombic to monoclinic) and magnetic (paramagnetic to antiferromagnetic) transitions as well, making the problem more interesting and complex at the same time. The noise is of the 1/f type and is Gaussian in the high temperature phase, however deviations are seen in the low temperature phases. Below the metal-insulator transition, noise magnitude increases by orders of magnitude: a sign of inhomogeneous electrical conduction as result of phase separation. This is further assured by the non-Gaussian noise signature. At very low temperatures (T < 50 K), the noise behavior switches between Gaussian and non-Gaussian over several hours, possibly arising from dynamically competing ground states. VO2 is one of the most widely studied strongly correlated oxides and is important from the fundamental physics point of view and for applications. Its transition from a metal to an insulator (MIT) with simple application of voltage is quite interesting. For use in applications, e.g. transistors, it is very important to have a clear understanding of the MIT. Equally important is the question of whether the thermally- and electrically-driven transitions have the same origin. In this thesis, we tried to answer this question by utilizing three different tuning parameters: temperature, voltage bias and strain. Our results point to an unusual noise behavior in the high-temperature metallic phase, and provide valuable insight into the transport dynamics of this material. CuxV2O5 exhibit a metal-insulator transition and, more interestingly, a superconductivity transition. Unlike VO2, copper vanadium bronzes are much less studied and many questions are still open, including the possibility of charge ordering transition, just like in other members of the vanadium family. In this thesis, we studied this material and found evidences for charge ordering transitions and possibly other transitions as well. The last material, NbSe3, is a prototypical example of charge density wave systems, where Peierls transitions exist. Here, we study the effects of contacts on resistance noise in the 1D limit. The study aimed to confirm that the electric field threshold is sample length independent, to find out if there is a relation between contact separation and the noise generated and to explore the characteristics of the contact noise. The results confirm that the electric field threshold is independent of the sample length. It was also found that the separation between the contacts does not affect the noise. Finally, the contact noise is of the 1/f-type and has a Gaussian distribution. These results are timely for future device applications utilizing NbSe3.

Effect of temperature on the population dynamics of Aedes aegypti

NASA Astrophysics Data System (ADS)

Yusoff, Nuraini; Tokachil, Mohd Najir

2015-10-01

Aedes aegypti is one of the main vectors in the transmission of dengue fever. Its abundance may cause the spread of the disease to be more intense. In the study of its biological life cycle, temperature was found to increase the development rate of each stage of this species and thus, accelerate the process of the development from egg to adult. In this paper, a Lefkovitch matrix model will be used to study the stage-structured population dynamics of Aedes aegypti. In constructing the transition matrix, temperature will be taken into account. As a case study, temperature recorded at the Subang Meteorological Station for year 2006 until 2010 will be used. Population dynamics of Aedes aegypti at maximum, average and minimum temperature for each year will be simulated and compared. It is expected that the higher the temperature, the faster the mosquito will breed. The result will be compared to the number of dengue fever incidences to see their relationship.

Convection Models for Ice-Water System: Dynamical Investigation of Phase Transition

NASA Astrophysics Data System (ADS)

Allu Peddinti, D.; McNamara, A. K.

2012-12-01

Ever since planetary missions of Voyager and Galileo revealed a dynamically altered surface of the icy moon Europa, a possible subsurface ocean under an icy shell has been speculated and surface features have been interpreted from an interior dynamics perspective. The physics of convection in a two phase water-ice system is governed by a wide set of physical parameters that include melting viscosity of ice, the variation of viscosity due to pressure and temperature, temperature contrast across and tidal heating within the system, and the evolving thickness of each layer. Due to the extreme viscosity contrast between liquid water and solid ice, it is not feasible to model the entire system to study convection. However, using a low-viscosity proxy (higher viscosity than the liquid water but much lower than solid ice) for the liquid phase provides a convenient approximation of the system, and allows for a relatively realistic representation of convection within the ice layer while also providing a self-consistent ice layer thickness that is a function of the thermal state of the system. In order to apply this method appropriately, we carefully examine the upper bound of viscosity required for the low-viscosity proxy to adequately represent the liquid phase. We identify upper bounds on the viscosity of the proxy liquid such that convective dynamics of the ice are not affected by further reductions of viscosity. Furthermore, we investigate how the temperature contrast across the system and viscosity contrast between liquid and ice control ice layer thickness. We also investigate ice shell thickening as a function of cooling, particularly how viscosity affects the conduction-to-convection transition within the ice shell. Finally, we present initial results that investigate the effects that latent heat of fusion (due to the ice-water phase transition) has on ice convection.

Universal depinning transition of domain walls in ultrathin ferromagnets

NASA Astrophysics Data System (ADS)

Diaz Pardo, R.; Savero Torres, W.; Kolton, A. B.; Bustingorry, S.; Jeudy, V.

2017-05-01

We present a quantitative and comparative study of magnetic-field-driven domain-wall depinning transition in different ferromagnetic ultrathin films over a wide range of temperature. We reveal a universal scaling function accounting for both drive and thermal effects on the depinning transition, including critical exponents. The consistent description we obtain for both the depinning and subthreshold thermally activated creep motion should shed light on the universal glassy dynamics of thermally fluctuating elastic objects pinned by disordered energy landscapes.

Ion transport mechanism in glasses: non-Arrhenius conductivity and nonuniversal features.

PubMed

Murugavel, S; Vaid, C; Bhadram, V S; Narayana, C

2010-10-28

In this article, we report non-Arrhenius behavior in the temperature-dependent dc conductivity of alkali ion conducting silicate glasses well below their glass transition temperature. In contrast to the several fast ion-conducting and binary potassium silicate glasses, these glasses show a positive deviation in the Arrhenius plot. The observed non-Arrhenius behavior is completely reproducible in nature even after prolonged annealing close to the glass transition temperature of the respective glass sample. These results are the manifestation of local structural changes of the silicate network with temperature and give rise to different local environments into which the alkali ions hop, revealed by in situ high-temperature Raman spectroscopy. Furthermore, the present study provides new insights into the strong link between the dynamics of the alkali ions and different sites associated with it in the glasses.

Nature of phase transitions in ammonium oxofluorovanadates, a vibrational spectroscopy study of (NH4)3VO2F4 and (NH4)3VOF5.

PubMed

Gerasimova, Yu V; Oreshonkov, A S; Laptash, N M; Vtyurin, A N; Krylov, A S; Shestakov, N P; Ershov, A A; Kocharova, A G

2017-04-05

Two ammonium oxofluorovanadates, (NH 4 ) 3 VO 2 F 4 and (NH 4 ) 3 VOF 5 , have been investigated by temperature-dependent infrared and Raman spectroscopy methods to determine the nature of phase transitions (PT) in these compounds. Dynamics of quasioctahedral groups was simulated within the framework of semi-empirical approach, which justified the cis-conformation of VO 2 F 4 3- (C 2v ) and the C 4v geometry of VOF 5 3- . The observed infrared and Raman spectra of both compounds at room temperature (RT) revealed the presence at least of two crystallographically independent octahedral groups. The first order PT at elevated temperatures is connected with a complete dynamic disordering of these groups with only single octahedral state. At lower temperatures, the octahedra are ordered and several octahedral states appear. This PT is the most pronounced in the case of (NH 4 ) 3 VOF 5 , when at least seven independent VOF 5 3- octahedra are present in the structure below 50K, in accordance with the Raman spectra. Ammonium groups do not take part in PTs at higher and room temperatures but their reorientational motion freezes at lower temperatures. Copyright © 2017. Published by Elsevier B.V.

Traction and lubricant film temperature as related to the glass transition temperature and solidification. [using infrared spectroscopy on EHD contacts

NASA Technical Reports Server (NTRS)

Lauer, J. L.; Peterkin, M. E.

1978-01-01

Does a traction fluid have to be a glass or solid under operating conditions. Infrared spectra on dynamic EHD contacts of several types of fluid were used to determine the surface and oil-film temperatures. Polarized spectral runs were made to study molecular alignment. Static glass transition pressures at appropriate temperatures were between 0.1 and 2.0 GPa, with the traction fluid showing the highest. In the EHD contact region, the traction fluid showed both the highest film temperatures as well as the greatest degree of molecular alignment. A plot of the difference between the film and surface temperatures vs shear rate resulted in a master plot valid for all the fluids. From this work, the authors propose a model of 'fluid' traction, where friction between parallel rough molecules provides the traction.

Heterogeneous to homogeneous melting transition visualized with ultrafast electron diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

The ultrafast laser excitation of matters leads to non-equilibrium states with complex solid-liquid phase transition dynamics. We used electron diffraction at mega-electronvolt energies to visualize the ultrafast melting of gold on the atomic scale length. For energy densities approaching the irreversible melting regime, we first observed heterogeneous melting on time scales of 100 ps to 1000 ps, transitioning to homogeneous melting that occurs catastrophically within 10-20 ps at higher energy densities. We showed evidence for the heterogeneous coexistence of solid and liquid. We determined the ion and electron temperature evolution and found superheated conditions. Our results constrain the electron-ion couplingmore » rate, determine the Debye temperature and reveal the melting sensitivity to nucleation seeds.« less

Relaxation dynamics and transformation kinetics of deeply supercooled water: Temperature, pressure, doping, and proton/deuteron isotope effects.

PubMed

Lemke, Sonja; Handle, Philip H; Plaga, Lucie J; Stern, Josef N; Seidl, Markus; Fuentes-Landete, Violeta; Amann-Winkel, Katrin; Köster, Karsten W; Gainaru, Catalin; Loerting, Thomas; Böhmer, Roland

2017-07-21

Above its glass transition, the equilibrated high-density amorphous ice (HDA) transforms to the low-density pendant (LDA). The temperature dependence of the transformation is monitored at ambient pressure using dielectric spectroscopy and at elevated pressures using dilatometry. It is found that near the glass transition temperature of deuterated samples, the transformation kinetics is 300 times slower than the structural relaxation, while for protonated samples, the time scale separation is at least 30 000 and insensitive to doping. The kinetics of the HDA to LDA transformation lacks a proton/deuteron isotope effect, revealing that this process is dominated by the restructuring of the oxygen network. The x-ray diffraction experiments performed on samples at intermediate transition stages reflect a linear combination of the LDA and HDA patterns implying a macroscopic phase separation, instead of a local intermixing of the two amorphous states.

Infrared reflectivity investigation of the phase transition sequence in Pr0.5Ca0.5MnO3

NASA Astrophysics Data System (ADS)

Ribeiro, J. L.; Vieira, L. G.; Gomes, I. T.; Araújo, J. P.; Tavares, P.; Almeida, B. G.

2016-06-01

This work reports an infrared reflectivity study of the phase transition sequence observed in Pr0.5Ca0.5MnO3. The need to measure over an extended spectral range in order to properly take into account the effects of the high frequency polaronic absorption is circumvented by adopting a simple approximate method, based on the asymmetry present in the Kramers Kronig inversion of the phonon spectrum. The temperature dependence of the phonon optical conductivity is then investigated by monitoring the behavior of three relevant spectral moments of the optical conductivity. This combined methodology allows us to disclose subtle effects of the orbital, charge and magnetic orders on the lattice dynamics of the compound. The characteristic transition temperatures inferred from the spectroscopic measurements are compared and correlated with those obtained from the temperature dependence of the induced magnetization and electrical resistivity.

Relaxation dynamics and transformation kinetics of deeply supercooled water: Temperature, pressure, doping, and proton/deuteron isotope effects

NASA Astrophysics Data System (ADS)

Lemke, Sonja; Handle, Philip H.; Plaga, Lucie J.; Stern, Josef N.; Seidl, Markus; Fuentes-Landete, Violeta; Amann-Winkel, Katrin; Köster, Karsten W.; Gainaru, Catalin; Loerting, Thomas; Böhmer, Roland

2017-07-01

Above its glass transition, the equilibrated high-density amorphous ice (HDA) transforms to the low-density pendant (LDA). The temperature dependence of the transformation is monitored at ambient pressure using dielectric spectroscopy and at elevated pressures using dilatometry. It is found that near the glass transition temperature of deuterated samples, the transformation kinetics is 300 times slower than the structural relaxation, while for protonated samples, the time scale separation is at least 30 000 and insensitive to doping. The kinetics of the HDA to LDA transformation lacks a proton/deuteron isotope effect, revealing that this process is dominated by the restructuring of the oxygen network. The x-ray diffraction experiments performed on samples at intermediate transition stages reflect a linear combination of the LDA and HDA patterns implying a macroscopic phase separation, instead of a local intermixing of the two amorphous states.

Disordering and dynamic self-organization in stoichiometric UO2 at high temperatures

NASA Astrophysics Data System (ADS)

Annamareddy, Ajay; Eapen, Jacob

2017-01-01

Neutron scattering experiments show significant oxygen disorder in UO2 at temperatures above 2000 K. The nature of the disorder, however, has not been ascertained with certainty. Using atomistic simulations and metrics from statistical mechanics we show that the oxygen anions predominantly hop from one native (tetrahedral) lattice site to another, above a characteristic temperature Tα (∼2000 K). Interestingly, we discover two types of disorder - the first one, which is a measure of the fraction of anions that are displaced from their native sites, portrays a monotonic increase with temperature and shows excellent conformity to neutron scattering data. The second metric based on the mean square displacement of the anions in an isoconfigurational ensemble demonstrates a dynamic self-organization behavior in which the anions are spatially correlated to those with similar mobility. This dynamic self-organization, however, experiences a non-monotonic variation with temperature depicting a maximum near the Bredig or λ-transition. We further establish that the thermodynamic metric cp/T, which is equal to the rate of change of entropy with temperature, is a key entropic indicator of the dynamic self-organization among the oxygen anions in UO2 at high temperatures.

Dynamical singularities of glassy systems in a quantum quench.

PubMed

Obuchi, Tomoyuki; Takahashi, Kazutaka

2012-11-01

We present a prototype of behavior of glassy systems driven by quantum dynamics in a quenching protocol by analyzing the random energy model in a transverse field. We calculate several types of dynamical quantum amplitude and find a freezing transition at some critical time. The behavior is understood by the partition-function zeros in the complex temperature plane. We discuss the properties of the freezing phase as a dynamical chaotic phase, which are contrasted to those of the spin-glass phase in the static system.

Dynamic mechanical analysis and organization/storage of data for polymetric materials

NASA Technical Reports Server (NTRS)

Rosenberg, M.; Buckley, W.

1982-01-01

Dynamic mechanical analysis was performed on a variety of temperature resistant polymers and composite resin matrices. Data on glass transition temperatures and degree of cure attained were derived. In addition a laboratory based computer system was installed and data base set up to allow entry of composite data. The laboratory CPU termed TYCHO is based on a DEC PDP 11/44 CPU with a Datatrieve relational data base. The function of TYCHO is integration of chemical laboratory analytical instrumentation and storage of chemical structures for modeling of new polymeric structures and compounds

Molecular dynamics simulation of melting of 2D glassy monatomic system

NASA Astrophysics Data System (ADS)

Nhu Tranh, Duong Thi; Van Hoang, Vo; Thu Hanh, Tran Thi

2018-01-01

The melting of two-dimensional (2D) glassy monatomic systems is studied using the molecular dynamics simulation with Lennard-Jones-Gauss interaction potential. The temperature dependence of various structural and dynamical properties of the systems during heating is analyzed and discussed via the radial distribution functions, the coordination number distributions, the ring statistics, the mobility of atoms and their clustering. Atomic mechanism of melting is also analyzed via tendency to increase mobility and breaking clusters of atoms upon heating. We found that melting of a 2D glass does not follow any theory of the melting of 2D crystals proposed in the past. The melting exhibits a homogeneous nature, i.e. liquid-like atoms occur homogeneously throughout the system and melting proceeds further leading to the formation of an entire liquid phase. In addition, we found a defined transition temperature region in which structural and dynamical properties of systems strongly change with increasing temperature.

Electron anions and the glass transition temperature.

PubMed

Johnson, Lewis E; Sushko, Peter V; Tomota, Yudai; Hosono, Hideo

2016-09-06

Properties of glasses are typically controlled by judicious selection of the glass-forming and glass-modifying constituents. Through an experimental and computational study of the crystalline, molten, and amorphous [Ca12Al14O32](2+) ⋅ (e(-))2, we demonstrate that electron anions in this system behave as glass modifiers that strongly affect solidification dynamics, the glass transition temperature, and spectroscopic properties of the resultant amorphous material. The concentration of such electron anions is a consequential control parameter: It invokes materials evolution pathways and properties not available in conventional glasses, which opens a unique avenue in rational materials design.

Light-induced metal-insulator transition in a switchable mirror.

PubMed

Hoekstra, A F; Roy, A S; Rosenbaum, T F; Griessen, R; Wijngaarden, R J; Koeman, N J

2001-06-04

Rare earth hydride films can be converted reversibly from metallic mirrors to insulating windows simply by changing the surrounding hydrogen gas pressure at room temperature. At low temperatures, in situ doping is not possible in this way as hydrogen cannot diffuse. However, our finding of persistent photoconductivity under ultraviolet illumination offers an attractive possibility to tune yttrium hydride through the T = 0 metal-insulator transition. Conductivity and Hall measurements are used to determine critical exponents. The unusually large value for the product of the static and dynamical critical exponents appears to signify the important role played by electron-electron interactions.

Electron anions and the glass transition temperature

DOE PAGES

Johnson, Lewis E.; Sushko, Peter V.; Tomota, Yudai; ...

2016-08-24

Properties of glasses are typically controlled by judicious selection of the glass-forming and glass-modifying constituents. Through an experimental and computational study of the crystalline, molten, and amorphous [Ca 12Al 14O 32] 2+ ∙ (e –) 2, we demonstrate that electron anions in this system behave as glass-modifiers that strongly affect solidification dynamics, the glass transition temperature, and spectroscopic properties of the resultant amorphous material. Concentration of such electron anions is a consequential control parameter: it invokes materials evolution pathways and properties not available in conventional glasses, which opens a new avenue in rational materials design.

Controlling protein molecular dynamics: How to accelerate folding while preserving the native state

NASA Astrophysics Data System (ADS)

Jensen, Christian H.; Nerukh, Dmitry; Glen, Robert C.

2008-12-01

The dynamics of peptides and proteins generated by classical molecular dynamics (MD) is described by using a Markov model. The model is built by clustering the trajectory into conformational states and estimating transition probabilities between the states. Assuming that it is possible to influence the dynamics of the system by varying simulation parameters, we show how to use the Markov model to determine the parameter values that preserve the folded state of the protein and at the same time, reduce the folding time in the simulation. We investigate this by applying the method to two systems. The first system is an imaginary peptide described by given transition probabilities with a total folding time of 1μs. We find that only small changes in the transition probabilities are needed to accelerate (or decelerate) the folding. This implies that folding times for slowly folding peptides and proteins calculated using MD cannot be meaningfully compared to experimental results. The second system is a four residue peptide valine-proline-alanine-leucine in water. We control the dynamics of the transitions by varying the temperature and the atom masses. The simulation results show that it is possible to find the combinations of parameter values that accelerate the dynamics and at the same time preserve the native state of the peptide. A method for accelerating larger systems without performing simulations for the whole folding process is outlined.

Ferroelectric to paraelectric phase transition mechanism in poled PVDF-TrFE copolymer films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pramanick, A.; T. Misture, Scott; Osti, Naresh C.

2017-11-01

Direct experimental insights into the structural and dynamical mechanisms for ferroelectric β to paraelectric α phase transition in a poled PVDF-TrFE copolymer is obtained from in situ x-ray diffraction and quasielastic neutron scattering measurements at high temperatures. It is observed that the β-to-α phase transition proceeds through two energetically distinct processes, which are identified here as the nucleation and growth of an intermediate γ phase with random skew linkages followed by a γ-to-α transition. The two energetically distinct microscopic processes can explain the stages of evolution for β-to-α phase transition observed from heat flow measurements.

Characterizing extrasolar planets

NASA Astrophysics Data System (ADS)

Brown, Timothy M.

Transiting extrasolar planets provide the best current opportunities for characterizing the physical properties of extrasolar planets. In this review, I first describe the geometry of planetary transits, and methods for detecting and refining the observations of such transits. I derive the methods by which transit light curves and radial velocity data can be analyzed to yield estimates of the planetary radius, mass, and orbital parameters. I also show how visible-light and infrared spectroscopy can be valuable tools for understanding the composition, temperature, and dynamics of the atmospheres of transiting planets. Finally, I relate the outcome of a participatory lecture-hall exercise relating to one term in the Drake equation, namely the lifetime of technical civilizations.

Warning signals for eruptive events in spreading fires

PubMed Central

Fox, Jerome M.; Whitesides, George M.

2015-01-01

Spreading fires are noisy (and potentially chaotic) systems in which transitions in dynamics are notoriously difficult to predict. As flames move through spatially heterogeneous environments, sudden shifts in temperature, wind, or topography can generate combustion instabilities, or trigger self-stabilizing feedback loops, that dramatically amplify the intensities and rates with which fires propagate. Such transitions are rarely captured by predictive models of fire behavior and, thus, complicate efforts in fire suppression. This paper describes a simple, remarkably instructive physical model for examining the eruption of small flames into intense, rapidly moving flames stabilized by feedback between wind and fire (i.e., “wind–fire coupling”—a mechanism of feedback particularly relevant to forest fires), and it presents evidence that characteristic patterns in the dynamics of spreading flames indicate when such transitions are likely to occur. In this model system, flames propagate along strips of nitrocellulose with one of two possible modes of propagation: a slow, structured mode, and a fast, unstructured mode sustained by wind–fire coupling. Experimental examination of patterns in dynamics that emerge near bifurcation points suggests that symptoms of critical slowing down (i.e., the slowed recovery of the system from perturbations as it approaches tipping points) warn of impending transitions to the unstructured mode. Findings suggest that slowing responses of spreading flames to sudden changes in environment (e.g., wind, terrain, temperature) may anticipate the onset of intense, feedback-stabilized modes of propagation (e.g., “blowup fires” in forests). PMID:25675491

Efficient dynamical correction of the transition state theory rate estimate for a flat energy barrier.

PubMed

Mökkönen, Harri; Ala-Nissila, Tapio; Jónsson, Hannes

2016-09-07

The recrossing correction to the transition state theory estimate of a thermal rate can be difficult to calculate when the energy barrier is flat. This problem arises, for example, in polymer escape if the polymer is long enough to stretch between the initial and final state energy wells while the polymer beads undergo diffusive motion back and forth over the barrier. We present an efficient method for evaluating the correction factor by constructing a sequence of hyperplanes starting at the transition state and calculating the probability that the system advances from one hyperplane to another towards the product. This is analogous to what is done in forward flux sampling except that there the hyperplane sequence starts at the initial state. The method is applied to the escape of polymers with up to 64 beads from a potential well. For high temperature, the results are compared with direct Langevin dynamics simulations as well as forward flux sampling and excellent agreement between the three rate estimates is found. The use of a sequence of hyperplanes in the evaluation of the recrossing correction speeds up the calculation by an order of magnitude as compared with the traditional approach. As the temperature is lowered, the direct Langevin dynamics simulations as well as the forward flux simulations become computationally too demanding, while the harmonic transition state theory estimate corrected for recrossings can be calculated without significant increase in the computational effort.

Warning signals for eruptive events in spreading fires.

PubMed

Fox, Jerome M; Whitesides, George M

2015-02-24

Spreading fires are noisy (and potentially chaotic) systems in which transitions in dynamics are notoriously difficult to predict. As flames move through spatially heterogeneous environments, sudden shifts in temperature, wind, or topography can generate combustion instabilities, or trigger self-stabilizing feedback loops, that dramatically amplify the intensities and rates with which fires propagate. Such transitions are rarely captured by predictive models of fire behavior and, thus, complicate efforts in fire suppression. This paper describes a simple, remarkably instructive physical model for examining the eruption of small flames into intense, rapidly moving flames stabilized by feedback between wind and fire (i.e., "wind-fire coupling"-a mechanism of feedback particularly relevant to forest fires), and it presents evidence that characteristic patterns in the dynamics of spreading flames indicate when such transitions are likely to occur. In this model system, flames propagate along strips of nitrocellulose with one of two possible modes of propagation: a slow, structured mode, and a fast, unstructured mode sustained by wind-fire coupling. Experimental examination of patterns in dynamics that emerge near bifurcation points suggests that symptoms of critical slowing down (i.e., the slowed recovery of the system from perturbations as it approaches tipping points) warn of impending transitions to the unstructured mode. Findings suggest that slowing responses of spreading flames to sudden changes in environment (e.g., wind, terrain, temperature) may anticipate the onset of intense, feedback-stabilized modes of propagation (e.g., "blowup fires" in forests).

Warning signals for eruptive events in spreading fires

DOE PAGES

Fox, Jerome M.; Whitesides, George M.

2015-02-09

Spreading fires are noisy (and potentially chaotic) systems in which transitions in dynamics are notoriously difficult to predict. As flames move through spatially heterogeneous environments, sudden shifts in temperature, wind, or topography can generate combustion instabilities, or trigger self-stabilizing feedback loops, that dramatically amplify the intensities and rates with which fires propagate. Such transitions are rarely captured by predictive models of fire behavior and, thus, complicate efforts in fire suppression. This study describes a simple, remarkably instructive physical model for examining the eruption of small flames into intense, rapidly moving flames stabilized by feedback between wind and fire (i.e., “wind–firemore » coupling”—a mechanism of feedback particularly relevant to forest fires), and it presents evidence that characteristic patterns in the dynamics of spreading flames indicate when such transitions are likely to occur. Here, in this model system, flames propagate along strips of nitrocellulose with one of two possible modes of propagation: a slow, structured mode, and a fast, unstructured mode sustained by wind–fire coupling. Experimental examination of patterns in dynamics that emerge near bifurcation points suggests that symptoms of critical slowing down (i.e., the slowed recovery of the system from perturbations as it approaches tipping points) warn of impending transitions to the unstructured mode. Lastly, findings suggest that slowing responses of spreading flames to sudden changes in environment (e.g., wind, terrain, temperature) may anticipate the onset of intense, feedback-stabilized modes of propagation (e.g., “blowup fires” in forests).« less

Warning signals for eruptive events in spreading fires

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fox, Jerome M.; Whitesides, George M.

Spreading fires are noisy (and potentially chaotic) systems in which transitions in dynamics are notoriously difficult to predict. As flames move through spatially heterogeneous environments, sudden shifts in temperature, wind, or topography can generate combustion instabilities, or trigger self-stabilizing feedback loops, that dramatically amplify the intensities and rates with which fires propagate. Such transitions are rarely captured by predictive models of fire behavior and, thus, complicate efforts in fire suppression. This study describes a simple, remarkably instructive physical model for examining the eruption of small flames into intense, rapidly moving flames stabilized by feedback between wind and fire (i.e., “wind–firemore » coupling”—a mechanism of feedback particularly relevant to forest fires), and it presents evidence that characteristic patterns in the dynamics of spreading flames indicate when such transitions are likely to occur. Here, in this model system, flames propagate along strips of nitrocellulose with one of two possible modes of propagation: a slow, structured mode, and a fast, unstructured mode sustained by wind–fire coupling. Experimental examination of patterns in dynamics that emerge near bifurcation points suggests that symptoms of critical slowing down (i.e., the slowed recovery of the system from perturbations as it approaches tipping points) warn of impending transitions to the unstructured mode. Lastly, findings suggest that slowing responses of spreading flames to sudden changes in environment (e.g., wind, terrain, temperature) may anticipate the onset of intense, feedback-stabilized modes of propagation (e.g., “blowup fires” in forests).« less

Heterogeneous Nature of Relaxation Dynamics of Room-Temperature Ionic Liquids (EMIm) 2[Co(NCS) 4] and (BMIm) 2[Co(NCS) 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hensel-Bielowka, Stella; Wojnarowska, Zaneta; Dzida, Marzena

2015-08-11

Dynamic crossover above T g has been recognized as a characteristic feature of molecular dynamics of liquids approaching glass transition. Experimentally, it is manifested as a change in Vogel–Fulcher–Tammann dependence or a breakdown of the Stokes–Einstein and related relations. In this study, we report the exception from this rather general pattern of behavior. By means of dielectric, ultrasonic, rheological, and calorimetric methods, dynamics of two good ionic conductors (BMIm) 2[Co(NCS) 4] and (EMIm) 2[Co(NCS) 4] of less common stoichiometry (2:1) was studied in a very broad temperature range. However, none of the mentioned dynamic changes was observed in the entiremore » studied temperature range. On the contrary, the single VFT and the same fractional Walden coefficient were found for conductivity and viscosity changes over 12 decades. Finally and moreover, ultrasonic studies revealed that the data at temperatures which cover the normal liquid region cannot be fitted by a single exponential decay, and the Cole–Cole function should be used instead.« less

Heterogeneous nature of relaxation dynamics of room-temperature ionic liquids (EMIm) 2[Co(NCS) 4] and (BMIm) 2[Co(NCS) 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hensel-Bielowka, Stella; Wojnarowska, Zaneta E.; Dzida, Marzena

2015-08-11

Dynamic crossover above T g has been recognized as a characteristic feature of molecular dynamics of liquids approaching glass transition. Experimentally, it is manifested as a change in Vogel Fulcher Tammann dependence or a breakdown of the Stokes Einstein and related relations. In this paper, we report the exception from this rather general pattern of behavior. By means of dielectric, ultrasonic, rheological, and calorimetric methods, dynamics of two good ionic conductors (BMIm) 2[Co(NCS) 4] and (EMIm) 2[Co(NCS) 4] of less common stoichiometry (2:1) was studied in a very broad temperature range. However, none of the mentioned dynamic changes was observedmore » in the entire studied temperature range. On the contrary, the single VFT and the same fractional Walden coefficient were found for conductivity and viscosity changes over 12 decades. Furthermore, ultrasonic studies revealed that the data at temperatures which cover the normal liquid region cannot be fitted by a single exponential decay, and the Cole Cole function should be used instead.« less

Preparation and Dynamic Mechanical Properties at Elevated Temperatures of a Tungsten/Glass Composite

NASA Astrophysics Data System (ADS)

Gao, Chong; Wang, Yingchun; Ma, Xueya; Liu, Keyi; Wang, Yubing; Li, Shukui; Cheng, Xingwang

2018-03-01

Experiments were conducted to prepare a borosilicate glass matrix composite containing 50 vol.% tungsten and examine its dynamic compressive behavior at elevated temperatures in the range of 450-775 °C. The results show that the homogenous microstructure of the tungsten/glass composite with relative density of 97% can be obtained by hot-pressing sintering at 800 °C for 1 h under pressure of 30 MPa. Dynamic compressive testing was carried out by a separate Hopkinson pressure bar system with a synchronous device. The results show that the peak stress decreases and the composite transforms from brittle to ductile in nature with testing temperature increasing from 450 to 750 °C. The brittle-ductile transition temperature is about 500 °C. Over 775 °C, the composite loses load-bearing capacity totally because of the excessive softening of the glass phase. In addition, the deformation and failure mechanism were analyzed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yujie; Gong, Sha; Wang, Zhen

The thermodynamic and kinetic parameters of an RNA base pair were obtained through a long-time molecular dynamics simulation of the opening-closing switch process of the base pair near its melting temperature. The thermodynamic parameters were in good agreement with the nearest-neighbor model. The opening rates showed strong temperature dependence, however, the closing rates showed only weak temperature dependence. The transition path time was weakly temperature dependent and was insensitive to the energy barrier. The diffusion constant exhibited super-Arrhenius behavior. The free energy barrier of breaking a single base stack results from the enthalpy increase, ΔH, caused by the disruption ofmore » hydrogen bonding and base-stacking interactions. The free energy barrier of base pair closing comes from the unfavorable entropy loss, ΔS, caused by the restriction of torsional angles. These results suggest that a one-dimensional free energy surface is sufficient to accurately describe the dynamics of base pair opening and closing, and the dynamics are Brownian.« less

Location-Specific Measurements of The Glass Transition Temperature in Fluorescently Labeled Diblock Copolymers

NASA Astrophysics Data System (ADS)

Christie, Dane; Register, Richard; Priestley, Rodney

Block copolymers can self-assemble into periodic structures containing a high internal surface area, nanoscale domain periods, and periodically varying composition profiles. Depending on their components, block copolymers may also exhibit variations in their dynamic properties e.g., glass transition temperature (Tg) across the domain period. Measuring the variation of Tg across the domain period of block copolymers has remained a significant challenge due to the nanometer length scale of the domain period. Here we use fluorescence spectroscopy and the selective incorporation of a pyrene-containing methacrylate monomer at various positions along the chain to characterize the distribution of glass transition temperatures across the domain period of an amorphous block copolymer. The pyrene-containing monomer location is determined from the monomer segment distribution calculated using self-consistent field theory. Our model system is a lamella-forming diblock copolymer of poly(butyl methacrylate - b- methyl methacrylate). We show that Tg is asymmetrically distributed across the interface; as the interface is approached, larger gradients in Tg exist in the hard PMMA-rich domain than in the soft PBMA-rich domain. By characterizing Tg of PBMA or PMMA interfacial segments, we show that polymer dynamics at the interface are heterogeneous; there is a 15 K difference in Tg measured between PBMA interfacial segments and PMMA interfacial segments.

Raman scattering boson peak and differential scanning calorimetry studies of the glass transition in tellurium-zinc oxide glasses.

PubMed

Stavrou, E; Tsiantos, C; Tsopouridou, R D; Kripotou, S; Kontos, A G; Raptis, C; Capoen, B; Bouazaoui, M; Turrell, S; Khatir, S

2010-05-19

Raman scattering and differential scanning calorimetry (DSC) measurements have been carried out on four mixed tellurium-zinc oxide (TeO(2))(1 - x)(ZnO)(x) (x = 0.1, 0.2, 0.3, 0.4) glasses under variable temperature, with particular attention being given to the respective glass transition region. From the DSC measurements, the glass transition temperature T(g) has been determined for each glass, showing a monotonous decrease of T(g) with increasing ZnO content. The Raman study is focused on the low-frequency band of the glasses, the so-called boson peak (BP), whose frequency undergoes an abrupt decrease at a temperature T(d) very close to the respective T(g) values obtained by DSC. These results show that the BP is highly sensitive to dynamical effects over the glass transition and provides a means for an equally reliable (to DSC) determination of T(g) in tellurite glasses and other network glasses. The discontinuous temperature dependence of the BP frequency at the glass transition, along with the absence of such a behaviour by the high-frequency Raman bands (due to local atomic vibrations), indicates that marked changes of the medium range order (MRO) occur at T(g) and confirms the correlation between the BP and the MRO of glasses.

Modification of the mechanical behavior in the glass transition region of poly(lactic acid) (PLA) through catalyzed reactive extrusion with poly(carbonate) (PC)

NASA Astrophysics Data System (ADS)

Phuong, Vu Thanh; Coltelli, Maria-Beatrice; Anguillesi, Irene; Cinelli, Patrizia; Lazzeri, Andrea

2014-05-01

In order to improve the thermal stability of PLA based materials the strategy of blending it with poly(carbonate) of bisphenol A (PC), having a higher glass transition temperature, was followed and PLA/PC blends with different compositions, obtained also in the presence of an interchange reaction catalyst, Tetrabutylammonium tetraphenylborate (TBATPB) and triacetin were prepared by melt extrusion. The dynamical mechanical characterization showed an interesting change of the storage modulus behavior in the PLA glass transition region, evident exclusively in the catalyzed blends. In particular, a new peak in the Tanδ trend at a temperature in between the one of PLA and the one of PC was observed only in the blends obtained in the presence of triacetin and TBATPB. The height and maximum temperature of the peak was different after the annealing of samples at 80°C. The data, showing an interesting improvement of thermal stability above the PLA glass transition, were explained keeping into account the formation of PLA-PC copolymer during the reactive extrusion. Furthermore, the glass transition temperature of the copolymer as a function of composition was studied and the obtained trend was discussed by comparing with literature models developed for copolymers.

Thermomechanical analysis and durability of commercial micro-porous polymer Li-ion battery separators

NASA Astrophysics Data System (ADS)

Love, Corey T.

2011-03-01

Static and dynamic thermomechanical analysis was performed with a dynamic mechanical analyzer (DMA) to identify thermal and mechanical transitions for commercially available polymer separators under mechanical loading. Clear transitions in deformation mode were observed at elevated temperatures. These transitions identified the onset of separator "shutdown" which occurred at temperatures below the polymer melting point. Mechanical loading direction was critical to the overall integrity of the separator. Anisotropic separators (Celgard 2320, 2400 and 2500) were mechanically limited when pulled in tensile in the transverse direction. The anisotropy of these separators is a result of the dry technique used to manufacture the micro-porous membranes. Separators prepared using the wet technique (Entek Gold LP) behaved more uniformly, or biaxially, where all mechanical properties were nearly identical within the separator plane. The information provided by the DMA can also be useful for predicting the long-term durability of polymer separators in lithium-ion batteries exposed to electrolyte (solvent and salt), thermal fluctuations and electrochemical cycling. Small losses in mechanical integrity were observed for separators exposed to the various immersion environments over the 4-week immersion time.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Borreguero, Jose M.; Mamontov, Eugene

Here, the calorimetric glass-transition temperature of water is 136 K, but extrapolation of thermodynamic and relaxation properties of water from ambient temperature to below its homogeneous nucleation temperature T H = 235 K predicts divergence at T S = 228 K. The “no-man’s land” between the T H and glassy water crystallization temperature of 150 K, which is encountered on warming up from the vitrified state, precludes a straightforward reconciliation of the two incompatible temperature dependences of water properties, above 235 K and below 150 K. The addition of lithium chloride to water allows bypassing both T H and Tmore » S on cooling, resulting in the dynamics with no features except the calorimetric glass transition, still at 136 K. We show that lithium chloride prevents hydrogen-bonding network completion in water on cooling, as manifested, in particular, in changing microscopic diffusion mechanism of the water molecules. Thus thermodynamic and relaxation peculiarities exhibited by pure water on cooling to its glass transition, such as the existence of the T H and T S, must be associated specifically with the hydrogen-bonding network.« less

Shear melting and high temperature embrittlement: theory and application to machining titanium.

PubMed

Healy, Con; Koch, Sascha; Siemers, Carsten; Mukherji, Debashis; Ackland, Graeme J

2015-04-24

We describe a dynamical phase transition occurring within a shear band at high temperature and under extremely high shear rates. With increasing temperature, dislocation deformation and grain boundary sliding are supplanted by amorphization in a highly localized nanoscale band, which allows for massive strain and fracture. The mechanism is similar to shear melting and leads to liquid metal embrittlement at high temperature. From simulation, we find that the necessary conditions are lack of dislocation slip systems, low thermal conduction, and temperature near the melting point. The first two are exhibited by bcc titanium alloys, and we show that the final one can be achieved experimentally by adding low-melting-point elements: specifically, we use insoluble rare earth metals (REMs). Under high shear, the REM becomes mixed with the titanium, lowering the melting point within the shear band and triggering the shear-melting transition. This in turn generates heat which remains localized in the shear band due to poor heat conduction. The material fractures along the shear band. We show how to utilize this transition in the creation of new titanium-based alloys with improved machinability.

Molecular modeling of polycarbonate materials: Glass transition and mechanical properties

NASA Astrophysics Data System (ADS)

Palczynski, Karol; Wilke, Andreas; Paeschke, Manfred; Dzubiella, Joachim

2017-09-01

Linking the experimentally accessible macroscopic properties of thermoplastic polymers to their microscopic static and dynamic properties is a key requirement for targeted material design. Classical molecular dynamics simulations enable us to study the structural and dynamic behavior of molecules on microscopic scales, and statistical physics provides a framework for relating these properties to the macroscopic properties. We take a first step toward creating an automated workflow for the theoretical prediction of thermoplastic material properties by developing an expeditious method for parameterizing a simple yet surprisingly powerful coarse-grained bisphenol-A polycarbonate model which goes beyond previous coarse-grained models and successfully reproduces the thermal expansion behavior, the glass transition temperature as a function of the molecular weight, and several elastic properties.

Reaching extended length-scales with temperature-accelerated dynamics

NASA Astrophysics Data System (ADS)

Amar, Jacques G.; Shim, Yunsic

2013-03-01

In temperature-accelerated dynamics (TAD) a high-temperature molecular dynamics (MD) simulation is used to accelerate the search for the next low-temperature activated event. While TAD has been quite successful in extending the time-scales of simulations of non-equilibrium processes, due to the fact that the computational work scales approximately as the cube of the number of atoms, until recently only simulations of relatively small systems have been carried out. Recently, we have shown that by combining spatial decomposition with our synchronous sublattice algorithm, significantly improved scaling is possible. However, in this approach the size of activated events is limited by the processor size while the dynamics is not exact. Here we discuss progress in developing an alternate approach in which high-temperature parallel MD along with localized saddle-point (LSAD) calculations, are used to carry out TAD simulations without restricting the size of activated events while keeping the dynamics ``exact'' within the context of harmonic transition-state theory. In tests of our LSAD method applied to Ag/Ag(100) annealing and Cu/Cu(100) growth simulations we find significantly improved scaling of TAD, while maintaining a negligibly small error in the energy barriers. Supported by NSF DMR-0907399.

Impact of hydration and temperature history on the structure and dynamics of lignin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vural, Derya; Gainaru, C.; O'Neill, Hugh Michael

The full utilization of plant biomass for the production of energy and novel materials often involves high temperature treatment. Examples include melt spinning of lignin for manufacturing low-cost carbon fiber and the relocalization of lignin to increase the accessibility of cellulose for production of biofuels. These temperature-induced effects arise from poorly understood changes in lignin flexibility. Here, we combine molecular dynamics simulations with neutron scattering and dielectric spectroscopy experiments to probe the dependence of lignin dynamics on hydration and thermal history. We find a dynamical and structural hysteresis: at a given temperature, the lignin molecules are more expanded and theirmore » dynamics faster when the lignin is cooled than when heated. The structural hysteresis is more pronounced for dry lignin. The difference in dynamics, however, follows a different trend, it is found to be more significant at high temperatures and high hydration levels. The simulations also reveal syringyl units to be more dynamic than guiacyl. The results provide an atomic-detailed description of lignin dynamics, important for understanding lignin role in plant cell wall mechanics and for rationally improving lignin processing. The lignin glass transition, at which the polymer softens, is lower when lignin is cooled than when heated, therefore extending the cooling phase of processing and shortening the heating phase may offer ways to lower processing costs.« less

Impact of hydration and temperature history on the structure and dynamics of lignin

DOE PAGES

Vural, Derya; Gainaru, C.; O'Neill, Hugh Michael; ...

2018-03-16

The full utilization of plant biomass for the production of energy and novel materials often involves high temperature treatment. Examples include melt spinning of lignin for manufacturing low-cost carbon fiber and the relocalization of lignin to increase the accessibility of cellulose for production of biofuels. These temperature-induced effects arise from poorly understood changes in lignin flexibility. Here, we combine molecular dynamics simulations with neutron scattering and dielectric spectroscopy experiments to probe the dependence of lignin dynamics on hydration and thermal history. We find a dynamical and structural hysteresis: at a given temperature, the lignin molecules are more expanded and theirmore » dynamics faster when the lignin is cooled than when heated. The structural hysteresis is more pronounced for dry lignin. The difference in dynamics, however, follows a different trend, it is found to be more significant at high temperatures and high hydration levels. The simulations also reveal syringyl units to be more dynamic than guiacyl. The results provide an atomic-detailed description of lignin dynamics, important for understanding lignin role in plant cell wall mechanics and for rationally improving lignin processing. The lignin glass transition, at which the polymer softens, is lower when lignin is cooled than when heated, therefore extending the cooling phase of processing and shortening the heating phase may offer ways to lower processing costs.« less

Simulation of Z(3) walls and string production via bubble nucleation in a quark-hadron transition

NASA Astrophysics Data System (ADS)

Gupta, Uma Shankar; Mohapatra, Ranjita K.; Srivastava, Ajit M.; Tiwari, Vivek K.

2010-10-01

We study the dynamics of confinement-deconfinement phase transition in the context of relativistic heavy-ion collisions within the framework of effective models for the Polyakov loop order parameter. We study the formation of Z(3) walls and associated strings in the initial transition from the confining (hadronic) phase to the deconfining [quark-gluon plasma (QGP)] phase via the so-called Kibble mechanism. Essential physics of the Kibble mechanism is contained in a sort of domain structure arising after any phase transition which represents random variation of the order parameter at distances beyond the typical correlation length. We implement this domain structure by using the Polyakov loop effective model with a first order phase transition and confine ourselves with temperature/time ranges so that the first order confinement-deconfinement transition proceeds via bubble nucleation, leading to a well defined domain structure. The formation of Z(3) walls and associated strings results from the coalescence of QGP bubbles expanding in the confining background. We investigate the evolution of the Z(3) wall and string network. We also calculate the energy density fluctuations associated with Z(3) wall network and strings which decay away after the temperature drops below the quark-hadron transition temperature during the expansion of QGP. We discuss evolution of these quantities with changing temperature via Bjorken’s hydrodynamical model and discuss possible experimental signatures resulting from the presence of Z(3) wall network and associate strings.

Simulation of Z(3) walls and string production via bubble nucleation in a quark-hadron transition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gupta, Uma Shankar; Tiwari, Vivek K.; Mohapatra, Ranjita K.

2010-10-01

We study the dynamics of confinement-deconfinement phase transition in the context of relativistic heavy-ion collisions within the framework of effective models for the Polyakov loop order parameter. We study the formation of Z(3) walls and associated strings in the initial transition from the confining (hadronic) phase to the deconfining [quark-gluon plasma (QGP)] phase via the so-called Kibble mechanism. Essential physics of the Kibble mechanism is contained in a sort of domain structure arising after any phase transition which represents random variation of the order parameter at distances beyond the typical correlation length. We implement this domain structure by using themore » Polyakov loop effective model with a first order phase transition and confine ourselves with temperature/time ranges so that the first order confinement-deconfinement transition proceeds via bubble nucleation, leading to a well defined domain structure. The formation of Z(3) walls and associated strings results from the coalescence of QGP bubbles expanding in the confining background. We investigate the evolution of the Z(3) wall and string network. We also calculate the energy density fluctuations associated with Z(3) wall network and strings which decay away after the temperature drops below the quark-hadron transition temperature during the expansion of QGP. We discuss evolution of these quantities with changing temperature via Bjorken's hydrodynamical model and discuss possible experimental signatures resulting from the presence of Z(3) wall network and associate strings.« less

Fluctuation driven electroweak phase transition

NASA Technical Reports Server (NTRS)

Gleiser, Marcelo; Kolb, Edward W.

1991-01-01

We examine the dynamics of the electroweak phase transition in the early Universe. For Higgs masses in the range 46 less than or = M sub H less than or = 150 GeV and top quark masses less than 200 GeV, regions of symmetric and asymmetric vacuum coexist to below the critical temperature, with thermal equilibrium between the two phases maintained by fluctuations of both phases. We propose that the transition to the asymmetric vacuum is completed by percolation of these subcritical fluctuations. Our results are relevant to scenarios of baryogenesis that invoke a weakly first-order phase transition at the electroweak scale.

Fluctuation-driven electroweak phase transition. [in early universe

NASA Technical Reports Server (NTRS)

Gleiser, Marcelo; Kolb, Edward W.

1992-01-01

We examine the dynamics of the electroweak phase transition in the early Universe. For Higgs masses in the range 46 less than or = M sub H less than or = 150 GeV and top quark masses less than 200 GeV, regions of symmetric and asymmetric vacuum coexist to below the critical temperature, with thermal equilibrium between the two phases maintained by fluctuations of both phases. We propose that the transition to the asymmetric vacuum is completed by percolation of these subcritical fluctuations. Our results are relevant to scenarios of baryogenesis that invoke a weakly first-order phase transition at the electroweak scale.

Ultra-slow dynamics in low density amorphous ice revealed by deuteron NMR: indication of a glass transition.

PubMed

Löw, Florian; Amann-Winkel, Katrin; Loerting, Thomas; Fujara, Franz; Geil, Burkhard

2013-06-21

The postulated glass-liquid transition of low density amorphous ice (LDA) is investigated with deuteron NMR stimulated echo experiments. Such experiments give access to ultra-slow reorientations of water molecules on time scales expected for structural relaxation of glass formers close to the glass-liquid transition temperature. An involved data analysis is necessary to account for signal contributions originating from a gradual crystallization to cubic ice. Even if some ambiguities remain, our findings support the view that pressure amorphized LDA ices are of glassy nature and undergo a glass-liquid transition before crystallization.

Band structure dynamics in indium wires

NASA Astrophysics Data System (ADS)

Chávez-Cervantes, M.; Krause, R.; Aeschlimann, S.; Gierz, I.

2018-05-01

One-dimensional indium wires grown on Si(111) substrates, which are metallic at high temperatures, become insulating below ˜100 K due to the formation of a charge density wave (CDW). The physics of this transition is not conventional and involves a multiband Peierls instability with strong interband coupling. This CDW ground state is readily destroyed with femtosecond laser pulses resulting in a light-induced insulator-to-metal phase transition. The current understanding of this transition remains incomplete, requiring measurements of the transient electronic structure to complement previous investigations of the lattice dynamics. Time- and angle-resolved photoemission spectroscopy with extreme ultraviolet radiation is applied to this end. We find that the transition from the insulating to the metallic band structure occurs within ˜660 fs, which is a fraction of the amplitude mode period. The long lifetime of the transient state (>100 ps) is attributed to trapping in a metastable state in accordance with previous work.

IR thermography for dynamic detection of laminar-turbulent transition

NASA Astrophysics Data System (ADS)

Simon, Bernhard; Filius, Adrian; Tropea, Cameron; Grundmann, Sven

2016-05-01

This work investigates the potential of infrared (IR) thermography for the dynamic detection of laminar-turbulent transition. The experiments are conducted on a flat plate at velocities of 8-14 m/s, and the transition of the laminar boundary layer to turbulence is forced by a disturbance source which is turned on and off with frequencies up to 10 Hz. Three different heating techniques are used to apply the required difference between fluid and structure temperature: a heated aluminum structure is used as an internal structure heating technique, a conductive paint acts as a surface bounded heater, while an IR heater serves as an example for an external heating technique. For comparison of all heating techniques, a normalization is introduced and the frequency response of the measured IR camera signal is analyzed. Finally, the different heating techniques are compared and consequences for the design of experiments on laminar-turbulent transition are discussed.

Femtosecond resolution of soft mode dynamics in structural phase transitions

NASA Technical Reports Server (NTRS)

Dougherty, Thomas P.; Wiederrecht, Gary P.; Nelson, Keith A.; Garrett, Mark H.; Jensen, Hans P.; Warde, Cardinal

1992-01-01

The microscopic pathway along which ions or molecules in a crystal move during structural phase transition can often be described in terms of a collective vibrational mode of the lattice. In many cases, this mode, called a 'soft' phonon mode because of its characteristically low frequency near the phase transition temperature, is difficult to characterize through conventional frequency-domain spectroscopies such as light or neutron scattering. A femtosecond time-domain analog of light-scattering spectroscopy called impulsive stimulated Raman scattering (ISRS) has been used to examine the soft modes of two perovskite ferroelectric crystals. The low-frequency lattice dynamics of KNbO3 and BaTiO3 are clarified in a manner that permits critical evaluation of microscopic models for their ferroelectric transitions. The results illustrate the advantages of ISRS over conventional Raman spectroscopy of low-frequency, heavily damped soft modes.

Molecular Dynamics Simulations of a Cyclic DP-240 Amylose Fragment in a Periodic Cell: Glass Transition Temperature and Water Diffusion

USDA-ARS?s Scientific Manuscript database

Molecular dynamics simulations using AMB06C, an in-house carbohydrate force field, (NPT ensembles, 1atm) were carried out on a periodic cell that contained a cyclic-DP-240 amylose fragment and TIP3P water molecules. Molecular conformation and movement of the amylose fragment and water molecules at ...

Lattice dynamics and the nature of structural transitions in organolead halide perovskites

DOE PAGES

Comin, Riccardo; Crawford, Michael K.; Said, Ayman H.; ...

2016-09-09

Organolead halide perovskites are a family of hybrid organic-inorganic compounds whose remark- able optoelectronic properties have been under intensive scrutiny in recent years. Here we use inelastic X-ray scattering to study low-energy lattice excitations in single crystals of methylammonium lead iodide and bromide perovskites. Our ndings conrm the displacive nature of the cubic-to- tetragonal phase transition, which is further shown, using neutron and x-ray diraction, to be close to a tricritical point. The experimental sound speed, around 100-200 m/s, suggests that electron- phonon scattering is likely a limiting factor for further improvements in carrier mobility. Lastly, we detect quasistatic symmetry-breakingmore » nanodomains persisting well into the high-temperature cubic phase, possibly stabilized by local defects. These ndings reveal key structural properties of these materials, but also bear important implications for carrier dynamics across an extended temperature range relevant for photovoltaic applications.« less

Counting of fermions and spins in strongly correlated systems in and out of thermal equilibrium

NASA Astrophysics Data System (ADS)

Braungardt, Sibylle; Rodríguez, Mirta; Sen(de), Aditi; Sen, Ujjwal; Glauber, Roy J.; Lewenstein, Maciej

2011-01-01

Atom counting theory can be used to study the role of thermal noise in quantum phase transitions and to monitor the dynamics of a quantum system. We illustrate this for a strongly correlated fermionic system, which is equivalent to an anisotropic quantum XY chain in a transverse field and can be realized with cold fermionic atoms in an optical lattice. We analyze the counting statistics across the phase diagram in the presence of thermal fluctuations and during its thermalization when the system is coupled to a heat bath. At zero temperature, the quantum phase transition is reflected in the cumulants of the counting distribution. We find that the signatures of the crossover remain visible at low temperature and are obscured with increasing thermal fluctuations. We find that the same quantities may be used to scan the dynamics during the thermalization of the system.

Lattice dynamics and the nature of structural transitions in organolead halide perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Comin, Riccardo; Crawford, Michael K.; Said, Ayman H.

Organolead halide perovskites are a family of hybrid organic-inorganic compounds whose remark- able optoelectronic properties have been under intensive scrutiny in recent years. Here we use inelastic X-ray scattering to study low-energy lattice excitations in single crystals of methylammonium lead iodide and bromide perovskites. Our ndings conrm the displacive nature of the cubic-to- tetragonal phase transition, which is further shown, using neutron and x-ray diraction, to be close to a tricritical point. The experimental sound speed, around 100-200 m/s, suggests that electron- phonon scattering is likely a limiting factor for further improvements in carrier mobility. Lastly, we detect quasistatic symmetry-breakingmore » nanodomains persisting well into the high-temperature cubic phase, possibly stabilized by local defects. These ndings reveal key structural properties of these materials, but also bear important implications for carrier dynamics across an extended temperature range relevant for photovoltaic applications.« less

Tamoxifen-model membrane interactions: an FT-IR study

NASA Astrophysics Data System (ADS)

Boyar, Handan; Severcan, Feride

1997-06-01

The temperature- and concentration-induced effects of tamoxifen (TAM) on dipalmitoyl phosphatidylcholine (DPPC) model membranes were investigated by the Fourier transform-infrared (FT-IR) spectroscopic technique. An investigation of the C-H stretching region and the CO mode reveals that the inclusion of TAM changes the physical properties of the DPPC multibilayers by (i) shifting the main phase transition to lower temperatures; (ii) broadening the transition profile slightly; (iii) disordering the system in the gel and in the liquid crystalline phases; (iv) increasing the dynamics in the gel phase and decreasing the dynamics of the acyl chains in the liquid crystalline phase; (v) increasing the mobility of the terminal methyl group region of the bilayer in the gel phase and decreasing it in the liquid crystalline phase; (vi) increasing the frequency of the CO stretching mode both in the gel and in the liquid crystalline phases, i.e. non-bonding with carbonyl groups.

Measurements of observables during detonator function

NASA Astrophysics Data System (ADS)

Smilowitz, Laura; Henson, Bryan; Remelius, Dennis

Thermal explosion and detonation are two phenomena which can both occur as the response of explosives to thermal or mechanical insults. Thermal explosion is typically considered in the safety envelope and detonation is considered in the performance regime of explosive behavior. However, the two regimes are tied together by a phenomenon called deflagration to detonation transition (DDT). In this talk, I will discuss experiments on commercial detonators aimed at understanding the mechanism for energy release during detonator function. Diagnostic development towards measuring temperature, pressure, and density during the extreme conditions and time scales of detonation will be discussed. Our current ability to perform table-top dynamic radiography on functioning detonators will be described. Dynamic measurements of temperature, pressure, and density will be shown and discussion of the function of a detonator will be given in terms of our current understanding of deflagration, detonation, and the transition between the two.

Phase Coexistence in a Dynamic Phase Diagram.

PubMed

Gentile, Luigi; Coppola, Luigi; Balog, Sandor; Mortensen, Kell; Ranieri, Giuseppe A; Olsson, Ulf

2015-08-03

Metastability and phase coexistence are important concepts in colloidal science. Typically, the phase diagram of colloidal systems is considered at the equilibrium without the presence of an external field. However, several studies have reported phase transition under mechanical deformation. The reason behind phase coexistence under shear flow is not fully understood. Here, multilamellar vesicle (MLV)-to-sponge (L3 ) and MLV-to-Lα transitions upon increasing temperature are detected using flow small-angle neutron scattering techniques. Coexistence of Lα and MLV phases at 40 °C under shear flow is detected by using flow NMR spectroscopy. The unusual rheological behavior observed by studying the lamellar phase of a non-ionic surfactant is explained using (2) H NMR and diffusion flow NMR spectroscopy with the coexistence of planar lamellar-multilamellar vesicles. Moreover, a dynamic phase diagram over a wide range of temperatures is proposed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Addendum to the lattice dynamics of. gamma. -Ce

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stassis, C.; Loong, C.; McMasters, O.D.

1982-05-15

Inelastic neutron scattering techniques have been used to study the temperature dependence of the dispersion curves of ..gamma..-Ce. We find that the frequencies of all but the T (111), branches exhibit normal temperature dependence. Close to the zone boundary the frequencies of the T(111) branch, on the other hand, decrease with decreasing temperature, and at room temperature this branch exhibits a dip at the zone boundary. This anomalous behavior may be related to the fcc..-->..dhcp phase transition.

Molecular dynamics study about the effect of substrate temperature on a-Si:H structure

NASA Astrophysics Data System (ADS)

Luo, Yaorong; Gong, Hongyong; Zhou, Naigen; Huang, Haibin; Zhou, Lang

2018-01-01

Molecular dynamics simulation of the microstructure of hydrogenated amorphous silicon (a-Si:H) thin film with different substrate temperatures has been performed based on the Tersoff potential. The results showed that: the silicon thin film maintained amorphous structure in the substrate temperature range from 200 to 1000 K; high substrate temperature could smooth the surface. The first neighbour Voronoi polyhedron was dominated by the tetrahedron. When the substrate temperature increased, the content of tetrahedrons increased due to the transition from pentahedrons and hexahedrons to tetrahedrons. The change of the second neighbour Voronoi polyhedron could be classified into two cases: one case with low medium coordination number decreased as temperature increased, while the other one with high medium coordination number showed an opposite change tendency. It indicated that the local paracrystalline structure arrangement of the second neighbour atoms had been enhanced as substrate temperature rose.

Ion transport and structural dynamics in homologous ammonium and phosphonium-based room temperature ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Griffin, Philip J., E-mail: pgrif@seas.upenn.edu; Holt, Adam P.; Tsunashima, Katsuhiko

2015-02-28

Charge transport and structural dynamics in a homologous pair of ammonium and phosphonium based room temperature ionic liquids (ILs) have been characterized over a wide temperature range using broadband dielectric spectroscopy and quasi-elastic light scattering spectroscopy. We have found that the ionic conductivity of the phosphonium based IL is significantly enhanced relative to the ammonium homolog, and this increase is primarily a result of a lower glass transition temperature and higher ion mobility. Additionally, these ILs exhibit pronounced secondary relaxations which are strongly influenced by the atomic identity of the cation charge center. While the secondary relaxation in the phosphoniummore » IL has the expected Arrhenius temperature dependence characteristic of local beta relaxations, the corresponding relaxation process in the ammonium IL was found to exhibit a mildly non-Arrhenius temperature dependence in the measured temperature range—indicative of molecular cooperativity. These differences in both local and long-range molecular dynamics are a direct reflection of the subtly different inter-ionic interactions and mesoscale structures found in these homologous ILs.« less

Ion transport and structural dynamics in homologous ammonium and phosphonium-based room temperature ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Griffin, Phillip J.; Holt, Adam P.; Tsunashima, Katsuhiko

2015-02-01

Charge transport and structural dynamics in a homologous pair of ammonium and phosphonium based room temperature ionic liquids (ILs) have been characterized over a wide temperature range using broadband dielectric spectroscopy and quasi-elastic light scattering spectroscopy. We have found that the ionic conductivity of the phosphonium based IL is significantly enhanced relative to the ammonium homolog, and this increase is primarily a result of a lower glass transition temperature and higher ion mobility. Additionally, these ILs exhibit pronounced secondary relaxations which are strongly influenced by the atomic identity of the cation charge center. While the secondary relaxation in the phosphoniummore » IL has the expected Arrhenius temperature dependence characteristic of local beta relaxations, the corresponding relaxation process in the ammonium IL was found to exhibit a mildly non-Arrhenius temperature dependence in the measured temperature range-indicative of molecular cooperativity. These differences in both local and long-range molecular dynamics are a direct reflection of the subtly different inter-ionic interactions and mesoscale structures found in these homologous ILs.« less

Dynamical Generation of the Transition Zone in the Earth's Mantle

NASA Astrophysics Data System (ADS)

Hansen, U.; Stemmer, K.

2005-12-01

The internal structure of the Earth is made up by a series of layers, though it is unclear how many layers exist and if there are layers invisible to remote sensing techniques. The transition zone is likely to be a boundary layer separating the convective systems in the lower and upper mantle. It seems likely that currently there is some mass exchange across this boundary, rather than the two systems beeing strictly separated.a Double-diffusive convection(d.d.c) is a vital mechanism which can generate layered structure and may thus be an important mmical machinery behind the formation of the transition zone. Double-diffusive convection determines the dynamics of systems whose density is influenced by at least two components with different molecular diffusivities.In the mantle, composition and temperature play the role of those two components. By means of numerical experiments we demonstrate that under mantle relevant conditions d.d.c typically leads to the formation of a transition zone. The calculations encompass two- and three dimensional Cartesian geometries as well as fully 3D spherical domains. We have further included strongly temperature dependent viscosity and find that this leads to even more pronounced layering. In most cases a layered flow pattern emerges, where two layers with a transition zone in between resembles a quasistationary state. Thus, the transition zone can be the result of a self organization process of the convective flow in the mantle. The presence of a phase transition further helps to stabilize the boundary against overturning, even on a time scale on the order of the age of the Earth.

Two liquid states of matter: a dynamic line on a phase diagram.

PubMed

Brazhkin, V V; Fomin, Yu D; Lyapin, A G; Ryzhov, V N; Trachenko, K

2012-03-01

It is generally agreed that the supercritical region of a liquid consists of one single state (supercritical fluid). On the other hand, we show here that liquids in this region exist in two qualitatively different states: "rigid" and "nonrigid" liquids. Rigid to nonrigid transition corresponds to the condition τ≈τ(0), where τ is the liquid relaxation time and τ(0) is the minimal period of transverse quasiharmonic waves. This condition defines a new dynamic crossover line on the phase diagram and corresponds to the loss of shear stiffness of a liquid at all available frequencies and, consequently, to the qualitative change in many important liquid properties. We analyze this line theoretically as well as in real and model fluids and show that the transition corresponds to the disappearance of high-frequency sound, to the disappearance of roton minima, qualitative changes in the temperature dependencies of sound velocity, diffusion, viscous flow, and thermal conductivity, an increase in particle thermal speed to half the speed of sound, and a reduction in the constant volume specific heat to 2k(B) per particle. In contrast to the Widom line that exists near the critical point only, the new dynamic line is universal: It separates two liquid states at arbitrarily high pressure and temperature and exists in systems where liquid-gas transition and the critical point are absent altogether. We propose to call the new dynamic line on the phase diagram "Frenkel line".

VO2 film temperature dynamics at low-frequency current self-oscillations

NASA Astrophysics Data System (ADS)

Bortnikov, S. G.; Aliev, V. Sh.; Badmaeva, I. A.; Mzhelskiy, I. V.

2018-02-01

Low-frequency (˜2 Hz) current self-oscillations were first obtained in a millimeter-sized two-terminal planar device with a vanadium dioxide (VO2) film. The film temperature distribution dynamics was investigated within one oscillation period. It was established that the formation and disappearance of a conductive channel occur in a film in less than 60 ms with oscillation period 560 ms. The experimentally observed temperature in the channel region reached 413 K, being understated due to a low infrared microscope performance (integration time 10 ms). The VO2 film temperature distribution dynamics was simulated by solving a 2D problem of the electric current flow and heat transfer in the film. The calculation showed that the thermally initiated resistance switching in the film occurs in less than 4 ms at a channel temperature reaching ˜1000 K. The experimental results and simulation are consistent with the current self-oscillation mechanism based on the current pinching and dielectric relaxation in the VO2 film at the metal-insulator phase transition.

Revealing the glass transition in shape memory polymers using Brillouin spectroscopy.

PubMed

Steelman, Zachary A; Weems, Andrew C; Traverso, Andrew J; Szafron, Jason M; Maitland, Duncan J; Yakovlev, Vladislav V

2017-12-11

Emerging medical devices which employ shape memory polymers (SMPs) require precise measurements of the glass transition temperature (T g ) to ensure highly controlled shape recovery kinetics. Conventional techniques like differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) have limitations that prevent utilization for certain devices, including limited accuracy and the need for sacrificial samples. In this report, we employ an approach based on Brillouin spectroscopy to probe the glass transition of SMPs rapidly, remotely, and nondestructively. Further, we compare the T g obtained from Brillouin scattering with DMA- and DSC-measured T g to demonstrate the accuracy of Brillouin scattering for this application. We conclude that Brillouin spectroscopy is an accurate technique for obtaining the glass transition temperature of SMPs, aligning closely with the most common laboratory standards while providing a rapid, remote, and nondestructive method for the analysis of unique polymeric medical devices.

Revealing the glass transition in shape memory polymers using Brillouin spectroscopy

NASA Astrophysics Data System (ADS)

Steelman, Zachary A.; Weems, Andrew C.; Traverso, Andrew J.; Szafron, Jason M.; Maitland, Duncan J.; Yakovlev, Vladislav V.

2017-12-01

Emerging medical devices which employ shape memory polymers (SMPs) require precise measurements of the glass transition temperature (Tg) to ensure highly controlled shape recovery kinetics. Conventional techniques like differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) have limitations that prevent utilization for certain devices, including limited accuracy and the need for sacrificial samples. In this report, we employ an approach based on Brillouin spectroscopy to probe the glass transition of SMPs rapidly, remotely, and nondestructively. Further, we compare the Tg obtained from Brillouin scattering with DMA- and DSC-measured Tg to demonstrate the accuracy of Brillouin scattering for this application. We conclude that Brillouin spectroscopy is an accurate technique for obtaining the glass transition temperature of SMPs, aligning closely with the most common laboratory standards while providing a rapid, remote, and nondestructive method for the analysis of unique polymeric medical devices.

EFFECTS OF ONE WEEK TRITIUM EXPOSURE ON EPDM ELASTOMER

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clark, E

This report documents test results for the exposure of four formulations of EPDM (ethylene-propylene diene monomer) elastomer to tritium gas at one atmosphere for approximately one week and characterization of material property changes and changes to the exposure gas during exposure. All EPDM samples were provided by Los Alamos National Laboratory (LANL). Material properties that were characterized include mass, sample dimensions, appearance, flexibility, and dynamic mechanical properties. The glass transition temperature was determined by analysis of the dynamic mechanical property data per ASTM standards. No change of glass transition temperature due to the short tritium gas exposure was observed. Filledmore » and unfilled formulations of Dupont{reg_sign} Nordel{trademark} 1440 had a slightly higher glass transition temperature than filled and unfilled formulations of Uniroyal{reg_sign} Royalene{reg_sign} 580H; filled formulations had the same glass transition as unfilled. The exposed samples appeared the same as before exposure--there was no evidence of discoloration, and no residue on stainless steel spacers contacting the samples during exposure was observed. The exposed samples remained flexible--all formulations passed a break test without failing. The unique properties of polymers make them ideal for certain components in gas handling systems. Specifically, the resiliency of elastomers is ideal for sealing surfaces, for example in valves. EPDM, initially developed in the 1960s, is a hydrocarbon polymer used extensively for sealing applications. EPDM is used for its excellent combination of properties including high/low-temperature resistance, radiation resistance, aging resistance, and good mechanical properties. This report summarizes initial work to characterize effects of tritium gas exposure on samples of four types of EPDM elastomer: graphite filled and unfilled formulations of Nordel{trademark} 1440 and Royalene{reg_sign} 580H.« less

Effect of solvation-related interaction on the low-temperature dynamics of proteins

NASA Astrophysics Data System (ADS)

Zuo, Guanghong; Wang, Jun; Qin, Meng; Xue, Bin; Wang, Wei

2010-03-01

The effect of solvation-related interaction on the low-temperature dynamics of proteins is studied by taking into account the desolvation barriers in the interactions of native contacts. It is found out that about the folding transition temperature, the protein folds in a cooperative manner, and the water molecules are expelled from the hydrophobic core at the final stage in the folding process. At low temperature, however, the protein would generally be trapped in many metastable conformations with some water molecules frozen inside the protein. The desolvation takes an important role in these processes. The number of frozen water molecules and that of frozen states of proteins are further analyzed with the methods based on principal component analysis (PCA) and the clustering of conformations. It is found out that both the numbers of frozen water molecules and the frozen states of the protein increase quickly below a certain temperature. Especially, the number of frozen states of the protein increases exponentially following the decrease in the temperature, which resembles the basic features of glassy dynamics. Interestingly, it is observed that the freezing of water molecules and that of protein conformations happen at almost the same temperature. This suggests that the solvation-related interaction performs an important role for the low-temperature dynamics of the model protein.

Viscoelastic properties of addition-cured polyimides used in high temperature polymer matrix composites

NASA Technical Reports Server (NTRS)

Roberts, Gary D; Malarik, Diane C.; Robaidek, Jerrold O.

1991-01-01

Viscoelastic properties of the addition cured polyimide, PMR-15, were studied using dynamic mechanical and stress relaxation tests. For temperatures below the glass transition temperature, T sub g, the dynamic mechanical properties measured using a temperature scan rate of 10 C/min were strongly affected by the presence of absorbed moisture in the resin. Dynamic mechanical properties measured as a function of time during an isothermal hold provided an indication of chemical changes occurring in the resin. For temperatures above (T sub g + 20 C), the storage modulus increased continuously as a function of time indicating that additional crosslinking is occurring in the resin. Because of these changes in chemical structures, the stress relaxation modulus could not be measured over any useful time interval for temperatures above T sub g. For temperatures below T sub g, dynamic mechanical properties appeared to be unaffected by chemical changes for times exceeding 1 hr. Since the duration of the stress relaxation tests was less than 1 hr, the stress relaxation modulus could be measured. As long as the moisture content of the resin was less than 2 pct, stress relaxation curves measured at different temperatures could be superimposed using horizontal shifts along the log(time) axis with only small shifts along the vertical axis.

The characterisation of atomic structure and glass-forming ability of the Zr-Cu-Co metallic glasses studied by molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Celtek, M.; Sengul, S.

2018-03-01

In the present work, the glass formation process and structural properties of Zr50Cu50-xCox (0 ≤ x ≤ 50) bulk metallic glasses were investigated by a molecular dynamics simulation with the many body tight-binding potentials. The evolution of structure and glass formation process with temperature were discussed using the coordination number, the radial distribution functions, the volume-temperature curve, icosahedral short-range order, glass transition temperature, Voronoi analysis, Honeycutt-Andersen pair analysis technique and the distribution of bond-angles. Results indicate that adding Co causes similar responses on the nature of the Zr50Cu50-xCox (0 ≤ x ≤ 50) alloys except for higher glass transition temperature and ideal icosahedral type ordered local atomic environment. Also, the differences of the atomic radii play the key role in influencing the atomic structure of these alloys. Both Cu and Co atoms play a significant role in deciding the chemical and topological short-range orders of the Zr50Cu50-xCox ternary liquids and amorphous alloys. The glass-forming ability of these alloys is supported by the experimental observations reported in the literature up to now.

Phase transition analysis of V-shaped liquid crystal: Combined temperature-dependent FTIR and density functional theory approach

NASA Astrophysics Data System (ADS)

Singh, Swapnil; Singh, Harshita; Karthick, T.; Tandon, Poonam; Prasad, Veena

2018-01-01

Temperature-dependent Fourier transform infrared spectroscopy (FTIR) combined with density functional theory (DFT) is employed to study the mechanism of phase transitions of V-shaped bent-core liquid crystal. Since it has a large number of flexible bonds, one-dimensional potential energy scan (PES) was performed on the flexible bonds and predicted the most stable conformer I. A detailed analysis of vibrational normal modes of conformer I have been done on the basis of potential energy distribution. The good agreement between the calculated spectrum of conformer I and observed FTIR spectrum at room temperature validates our theoretical structure model. Furthermore, the prominent changes observed in the stretching vibrational bands of CH3/CH2, Cdbnd O, ring CC, ring CO, ring CH in-plane bending, and ring CH out-of-plane bending at Iso → nematic phase transition (at 155 °C) have been illustrated. However, the minor changes in the spectral features observed for the other phase transitions might be due to the shape or bulkiness of molecules. Combined FTIR and PES study beautifully explained the dynamics of the molecules, molecular realignment, H-bonding, and conformational changes at the phase transitions.

Excitations and relaxation dynamics in multiferroic GeV4S8 studied by terahertz and dielectric spectroscopy

NASA Astrophysics Data System (ADS)

Reschke, S.; Wang, Zhe; Mayr, F.; Ruff, E.; Lunkenheimer, P.; Tsurkan, V.; Loidl, A.

2017-10-01

We report on THz time-domain spectroscopy on multiferroic GeV4S8 , which undergoes orbital ordering at a Jahn-Teller transition at 30.5 K and exhibits antiferromagnetic order below 14.6 K. The THz experiments are complemented by dielectric experiments at audio and radio frequencies. We identify a low-lying excitation close to 0.5 THz, which is only weakly temperature dependent and probably corresponds to a molecular excitation within the electronic level scheme of the V4 clusters. In addition, we detect complex temperature-dependent behavior of a low-lying phononic excitation, closely linked to the onset of orbitally driven ferroelectricity. In the high-temperature cubic phase, which is paramagnetic and orbitally disordered, this excitation is of relaxational character becomes an overdamped Lorentzian mode in the orbitally ordered phase below the Jahn-Teller transition, and finally appears as well-defined phonon excitation in the antiferromagnetic state. Abrupt changes in the real and imaginary parts of the complex dielectric permittivity show that orbital ordering appears via a structural phase transition with strong first-order character and that the onset of antiferromagnetic order is accompanied by significant structural changes, which are of first-order character, too. Dielectric spectroscopy documents that at low frequencies, significant dipolar relaxations are present in the orbitally ordered, paramagnetic phase only. In contrast to the closely related GaV4S8 , this relaxation dynamics that most likely mirrors coupled orbital and polar fluctuations does not seem to be related to the dynamic processes detected in the THz regime.

The Role of Proximity Effects in Transition-Edge Sensor Design and Performance

NASA Technical Reports Server (NTRS)

Smith, Stephen J.

2012-01-01

Transition-edge sensor (TES) microcalorimeters and bolometers are under development by numerous groups worldwide for a variety of applications involving the measurement of particle and photon radiation. Recent experimental and theoretical progress has led to the realization that the fundamental physics of some TES systems involves the longitudinal proximity effect between the electrical bias contacts and the TES. As such, these devices are described as SS'S (or SN'S) weak-links exhibiting Fraunhofer-like magnetic field dependence, and exponential temperature dependence, of the critical current. These discoveries, for the first time, provide a realistic theoretical framework for predicting the resistive transition as a function of temperature, current and magnetic field. In this contribution, we review the latest theoretical and experimental results and investigate how proximity effects play an important role in determining the resistive transition characteristics, which ultimately determines the dynamic range and energy resolution of TES detectors. We investigate how these effects could be utilized in device design to engineer desired transition characteristics for a given application.

Static and dynamic dielectric properties of strongly polar liquids in the vicinity of first order and weakly first order phase transitions

NASA Astrophysics Data System (ADS)

Jadżyn, Jan; Czechowski, Grzegorz; Legrand, Christian; Douali, Redouane

2003-04-01

The paper presents the results of measurements of the linear dielectric properties of the compounds from the homologous series of alkylcyanobiphenyls (CnH2n+1PhPhCN, nCB) in the vicinity of the first order transition (from the isotropic liquid to the crystalline phase) of nonmesogenic nCB’s (n=2 4) and the weakly first order transition (from the isotropic liquid to the nematic phase) of 5CB. The experimental method for the separation of the critical part of the static permittivity derivative and the activation energy for rotation of the mesogenic molecules, in the vicinity of weakly first order phase transition, is proposed. It is shown that the critical temperature dependence of the permittivity and the activation energy can be described with a function of (T-T*)-α type, with the same values of the temperature of virtual transition of the second order (T*) and the critical exponent (α).

Liquid crystal droplet formation and anchoring dynamics in a microfluidic device

NASA Astrophysics Data System (ADS)

Steinhaus, Ben; Shen, Amy; Feng, James; Link, Darren

2004-11-01

Liquid crystal drops dispersed in a continuous phase of silicon oil are generated with a narrow distribution in droplet size in microfluidic devices both above and below the nematic to isotropic transition temperature. For these two cases, we observe not only the different LC droplet generation and coalescence dynamics, but also distinct droplet morphology. Our experiments show that the nematic liquid crystalline order is important for the LC droplet formation and anchoring dynamics.

Dynamic mechanical thermal analysis of hypromellose 2910 free films.

PubMed

Cespi, Marco; Bonacucina, Giulia; Mencarelli, Giovanna; Casettari, Luca; Palmieri, Giovanni Filippo

2011-10-01

It is common practice to coat oral solid dosage forms with polymeric materials for controlled release purposes or for practical and aesthetic reasons. Good knowledge of thermo-mechanical film properties or their variation as a function of polymer grade, type and amount of additives or preparation method is of prime importance in developing solid dosage forms. This work focused on the dynamic mechanical thermal characteristics of free films of hypromellose 2910 (also known as HPMC), prepared using three grades of this polymer from two different manufacturers, in order to assess whether polymer chain length or origin affects the mechanical or thermo-mechanical properties of the final films. Hypromellose free films were obtained by casting their aqueous solutions prepared at a specific concentrations in order to obtain the same viscosity for each. The films were stored at room temperature until dried and then examined using a dynamic mechanical analyser. The results of the frequency scans showed no significant differences in the mechanical moduli E' and E″ of the different samples when analysed at room temperature; however, the grade of the polymer affected material transitions during the heating process. Glass transition temperature, apparent activation energy and fragility parameters depended on polymer chain length, while the material brand showed little impact on film performance. Copyright © 2011 Elsevier B.V. All rights reserved.

Trehalose Mediated Inhibition of Lactate Dehydrogenase from Rabbit Muscle. The Application of Kramers' Theory in Enzyme Catalysis.

PubMed

Hernández-Meza, Juan M; Sampedro, José G

2018-04-19

Lactate dehydrogenase (LDH) catalyzes the reduction of pyruvate to lactate by using NADH. LDH kinetics has been proposed to be dependent on the dynamics of a loop over the active site. Kramers' theory has been useful in the study of enzyme catalysis dependent on large structural dynamics. In this work, LDH kinetics was studied in the presence of trehalose and at different temperatures. In the absence of trehalose, temperature increase raised exponentially the LDH V max and revealed a sigmoid transition of K m toward a low-affinity state similar to protein unfolding. Notably, LDH V max diminished when in the presence of trehalose, while pyruvate affinity increased and the temperature-mediated binding site transition was hindered. The effect of trehalose on k cat was viscosity dependent as described by Kramers' theory since V max correlated inversely with the viscosity of the medium. As a result, activation energy ( E a ) for pyruvate reduction was dramatically increased by trehalose presence. This work provides experimental evidence that the dynamics of a structural component in LDH is essential for catalysis, i.e., the closing of the loop on the active site. While the trehalose mediated-increased of pyruvate affinity is proposed to be due to the compaction and/or increase of structural order at the binding site.

The melting of stable glasses is governed by nucleation-and-growth dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jack, Robert L.; Berthier, Ludovic

2016-06-28

We discuss the microscopic mechanisms by which low-temperature amorphous states, such as ultrastable glasses, transform into equilibrium fluids, after a sudden temperature increase. Experiments suggest that this process is similar to the melting of crystals, thus differing from the behaviour found in ordinary glasses. We rationalize these observations using the physical idea that the transformation process takes place close to a “hidden” equilibrium first-order phase transition, which is observed in systems of coupled replicas. We illustrate our views using simulation results for a simple two-dimensional plaquette spin model, which is known to exhibit a range of glassy behaviour. Our resultsmore » suggest that nucleation-and-growth dynamics, as found near ordinary first-order transitions, is also the correct theoretical framework to analyse the melting of ultrastable glasses. Our approach provides a unified understanding of multiple experimental observations, such as propagating melting fronts, large kinetic stability ratios, and “giant” dynamic length scales. We also provide a comprehensive discussion of available theoretical pictures proposed in the context of ultrastable glass melting.« less

Imaging phase slip dynamics in micron-size superconducting rings

NASA Astrophysics Data System (ADS)

Polshyn, Hryhoriy; Naibert, Tyler R.; Budakian, Raffi

2018-05-01

We present a scanning probe technique for measuring the dynamics of individual fluxoid transitions in multiply connected superconducting structures. In these measurements, a small magnetic particle attached to the tip of a silicon cantilever is scanned over a micron-size superconducting ring fabricated from a thin aluminum film. We find that near the superconducting transition temperature of the aluminum, the dissipation and frequency of the cantilever changes significantly at particular locations where the tip-induced magnetic flux penetrating the ring causes the two lowest-energy fluxoid states to become nearly degenerate. In this regime, we show that changes in the cantilever frequency and dissipation are well-described by a stochastic resonance (SR) process, wherein small oscillations of the cantilever in the presence of thermally activated phase slips (TAPS) in the ring give rise to a dynamical force that modifies the mechanical properties of the cantilever. Using the SR model, we calculate the average fluctuation rate of the TAPS as a function of temperature over a 32-dB range in frequency, and we compare it to the Langer-Ambegaokar-McCumber-Halperin theory for TAPS in one-dimensional superconducting structures.

Neutron powder diffraction and molecular simulation study of the structural evolution of ammonia borane from 15 to 340 K.

PubMed

Hess, Nancy J; Schenter, Gregory K; Hartman, Michael R; Daemen, Luc L; Proffen, Thomas; Kathmann, Shawn M; Mundy, Christopher J; Hartl, Monika; Heldebrant, David J; Stowe, Ashley C; Autrey, Tom

2009-05-14

The structural behavior of (11)B-, (2)H-enriched ammonia borane, ND(3)(11)BD(3), over the temperature range from 15 to 340 K was investigated using a combination of neutron powder diffraction and ab initio molecular dynamics simulations. In the low temperature orthorhombic phase, the progressive displacement of the borane group under the amine group was observed leading to the alignment of the B-N bond near parallel to the c-axis. The orthorhombic to tetragonal structural phase transition at 225 K is marked by dramatic change in the dynamics of both the amine and borane group. The resulting hydrogen disorder is problematic to extract from the metrics provided by Rietveld refinement but is readily apparent in molecular dynamics simulation and in difference Fourier transform maps. At the phase transition, Rietveld refinement does indicate a disruption of one of two dihydrogen bonds that link adjacent ammonia borane molecules. Metrics determined by Rietveld refinement are in excellent agreement with those determined from molecular simulation. This study highlights the valuable insights added by coupled experimental and computational studies.

Melatonin induces opposite effects on order and dynamics of anionic DPPG model membranes

NASA Astrophysics Data System (ADS)

Sahin, Ipek; Severcan, Feride; Kazancı, Nadide

2007-05-01

The temperature and concentration induced effects of melatonin on anionic dipalmitoyl phosphatidylglycerol (DPPG) multilamellar liposomes (MLVs) were investigated by using Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC). The results show that melatonin does not perturb the phase transition profile, while a decrease in the main transition temperature ( Tm) is noticed at high melatonin concentrations (15, 24 and 30 mol %). Low concentrations of melatonin (3, 6 and 9 mol %) decrease the frequency of the CH 2 stretching mode, implying an ordering effect, whilst high concentrations of melatonin disorders system both in the gel and liquid crystalline phases. Furthermore, at low and high concentrations, melatonin also causes opposite effect on membrane dynamics. The bandwidth of the CH 2 stretching modes decreases at low concentrations, implying a decrease in the dynamics, while increasing it at high concentrations. Furthermore, it causes significant decrease in the frequency of the C dbnd O stretching and PO2- antisymmetric double bond stretching bands of DPPG for all concentrations both in the gel and liquid crystalline phases, which indicates strong hydrogen bonding around these functional groups.

Equation of state of paramagnetic CrN from ab initio molecular dynamics

NASA Astrophysics Data System (ADS)

Steneteg, Peter; Alling, Björn; Abrikosov, Igor A.

2012-04-01

The equation of state for chromium nitride has been debated in the literature in connection with a proposed collapse of its bulk modulus following the pressure-induced transition from the paramagnetic cubic phase to the antiferromagnetic orthorhombic phase [F. Rivadulla , Nature Mater.1476-112210.1038/nmat2549 8, 947 (2009); B. Alling , Nature Mater.1476-112210.1038/nmat2722 9, 283 (2010)]. Experimentally the measurements are complicated due to the low transition pressure, while theoretically the simulation of magnetic disorder represents a major challenge. Here a first-principles method is suggested for the calculation of thermodynamic properties of magnetic materials in their high-temperature paramagnetic phase. It is based on ab initio molecular dynamics and simultaneous redistributions of the disordered but finite local magnetic moments. We apply this disordered local moments molecular dynamics method to the case of CrN and simulate its equation of state. In particular the debated bulk modulus is calculated in the paramagnetic cubic phase and is shown to be very similar to that of the antiferromagnetic orthorhombic CrN phase for all considered temperatures.

Influence of composition fluctuations on the linear viscoelastic properties of symmetric diblock copolymers near the order-disorder transition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hickey, Robert J.; Gillard, Timothy M.; Lodge, Timothy P.

2015-08-28

Rheological evidence of composition fluctuations in disordered diblock copolymers near the order disorder transition (ODT) has been documented in the literature over the past three decades, characterized by a failure of time–temperature superposition (tTS) to reduce linear dynamic mechanical spectroscopy (DMS) data in the terminal viscoelastic regime to a temperature-independent form. However, for some materials, most notably poly(styrene-b-isoprene) (PS–PI), no signature of these rheological features has been found. We present small-angle X-ray scattering (SAXS) results on symmetric poly(cyclohexylethylene-b-ethylene) (PCHE–PE) diblock copolymers that confirm the presence of fluctuations in the disordered state and DMS measurements that also show no sign ofmore » the features ascribed to composition fluctuations. Assessment of DMS results published on five different diblock copolymer systems leads us to conclude that the effects of composition fluctuations can be masked by highly asymmetric block dynamics, thereby resolving a long-standing disagreement in the literature and reinforcing the importance of mechanical contrast in understanding the dynamics of ordered and disordered block polymers.« less

Athermal brittle-to-ductile transition in amorphous solids.

PubMed

Dauchot, Olivier; Karmakar, Smarajit; Procaccia, Itamar; Zylberg, Jacques

2011-10-01

Brittle materials exhibit sharp dynamical fractures when meeting Griffith's criterion, whereas ductile materials blunt a sharp crack by plastic responses. Upon continuous pulling, ductile materials exhibit a necking instability that is dominated by a plastic flow. Usually one discusses the brittle to ductile transition as a function of increasing temperature. We introduce an athermal brittle to ductile transition as a function of the cutoff length of the interparticle potential. On the basis of extensive numerical simulations of the response to pulling the material boundaries at a constant speed we offer an explanation of the onset of ductility via the increase in the density of plastic modes as a function of the potential cutoff length. Finally we can resolve an old riddle: In experiments brittle materials can be strained under grip boundary conditions and exhibit a dynamic crack when cut with a sufficiently long initial slot. Mysteriously, in molecular dynamics simulations it appeared that cracks refused to propagate dynamically under grip boundary conditions, and continuous pulling was necessary to achieve fracture. We argue that this mystery is removed when one understands the distinction between brittle and ductile athermal amorphous materials.

Ab Initio Calculations of Ultrashort Carrier Dynamics in Two-Dimensional Materials: Valley Depolarization in Single-Layer WSe2

NASA Astrophysics Data System (ADS)

Molina-Sánchez, Alejandro; Sangalli, Davide; Wirtz, Ludger; Marini, Andrea

2017-08-01

In single-layer WSe$_2$, a paradigmatic semiconducting transition metal dichalcogenide, a circularly polarized laser field can selectively excite electronic transitions in one of the inequivalent $K^{\\pm}$ valleys. Such selective valley population corresponds to a pseudospin polarization. This can be used as a degree of freedom in a valleytronic device provided that the time scale for its depolarization is sufficiently large. Yet, the mechanism behind the valley depolarization still remains heavily debated. Recent time-dependent Kerr experiments have provided an accurate way to visualize the valley dynamics by measuring the rotation of a linearly polarized probe pulse applied after a circularly polarized pump pulse. We present here a clear, accurate and parameter-free description of the valley dynamics. By using an atomistic, ab initio, approach we fully disclose the elemental mechanisms that dictate the depolarization effects. Our results are in excellent agreement with recent time-dependent Kerr experiments. We explain the Kerr dynamics and its temperature dependence in terms of electron-phonon mediated processes that induce spin-flip inter-valley transitions.

Thermodynamic precursors, liquid-liquid transitions, dynamic and topological anomalies in densified liquid germania

NASA Astrophysics Data System (ADS)

Pacaud, F.; Micoulaut, M.

2015-08-01

The thermodynamic, dynamic, structural, and rigidity properties of densified liquid germania (GeO2) have been investigated using classical molecular dynamics simulation. We construct from a thermodynamic framework an analytical equation of state for the liquid allowing the possible detection of thermodynamic precursors (extrema of the derivatives of the free energy), which usually indicate the possibility of a liquid-liquid transition. It is found that for the present germania system, such precursors and the possible underlying liquid-liquid transition are hidden by the slowing down of the dynamics with decreasing temperature. In this respect, germania behaves quite differently when compared to parent tetrahedral systems such as silica or water. We then detect a diffusivity anomaly (a maximum of diffusion with changing density/volume) that is strongly correlated with changes in coordinated species, and the softening of bond-bending (BB) topological constraints that decrease the liquid rigidity and enhance transport. The diffusivity anomaly is finally substantiated from a Rosenfeld-type scaling law linked to the pair correlation entropy, and to structural relaxation.

Noise-induced transitions and shifts in a climate-vegetation feedback model.

PubMed

Alexandrov, Dmitri V; Bashkirtseva, Irina A; Ryashko, Lev B

2018-04-01

Motivated by the extremely important role of the Earth's vegetation dynamics in climate changes, we study the stochastic variability of a simple climate-vegetation system. In the case of deterministic dynamics, the system has one stable equilibrium and limit cycle or two stable equilibria corresponding to two opposite (cold and warm) climate-vegetation states. These states are divided by a separatrix going across a point of unstable equilibrium. Some possible stochastic scenarios caused by different externally induced natural and anthropogenic processes inherit properties of deterministic behaviour and drastically change the system dynamics. We demonstrate that the system transitions across its separatrix occur with increasing noise intensity. The climate-vegetation system therewith fluctuates, transits and localizes in the vicinity of its attractor. We show that this phenomenon occurs within some critical range of noise intensities. A noise-induced shift into the range of smaller global average temperatures corresponding to substantial oscillations of the Earth's vegetation cover is revealed. Our analysis demonstrates that the climate-vegetation interactions essentially contribute to climate dynamics and should be taken into account in more precise and complex models of climate variability.

A molecular dynamics approach for predicting the glass transition temperature and plasticization effect in amorphous pharmaceuticals.

PubMed

Gupta, Jasmine; Nunes, Cletus; Jonnalagadda, Sriramakamal

2013-11-04

The objectives of this study were as follows: (i) To develop an in silico technique, based on molecular dynamics (MD) simulations, to predict glass transition temperatures (Tg) of amorphous pharmaceuticals. (ii) To computationally study the effect of plasticizer on Tg. (iii) To investigate the intermolecular interactions using radial distribution function (RDF). Amorphous sucrose and water were selected as the model compound and plasticizer, respectively. MD simulations were performed using COMPASS force field and isothermal-isobaric ensembles. The specific volumes of amorphous cells were computed in the temperature range of 440-265 K. The characteristic "kink" observed in volume-temperature curves, in conjunction with regression analysis, defined the Tg. The MD computed Tg values were 367 K, 352 K and 343 K for amorphous sucrose containing 0%, 3% and 5% w/w water, respectively. The MD technique thus effectively simulated the plasticization effect of water; and the corresponding Tg values were in reasonable agreement with theoretical models and literature reports. The RDF measurements revealed strong hydrogen bond interactions between sucrose hydroxyl oxygens and water oxygen. Steric effects led to weak interactions between sucrose acetal oxygens and water oxygen. MD is thus a powerful predictive tool for probing temperature and water effects on the stability of amorphous systems during drug development.

Phase transitions in Ising models on directed networks

NASA Astrophysics Data System (ADS)

Lipowski, Adam; Ferreira, António Luis; Lipowska, Dorota; Gontarek, Krzysztof

2015-11-01

We examine Ising models with heat-bath dynamics on directed networks. Our simulations show that Ising models on directed triangular and simple cubic lattices undergo a phase transition that most likely belongs to the Ising universality class. On the directed square lattice the model remains paramagnetic at any positive temperature as already reported in some previous studies. We also examine random directed graphs and show that contrary to undirected ones, percolation of directed bonds does not guarantee ferromagnetic ordering. Only above a certain threshold can a random directed graph support finite-temperature ferromagnetic ordering. Such behavior is found also for out-homogeneous random graphs, but in this case the analysis of magnetic and percolative properties can be done exactly. Directed random graphs also differ from undirected ones with respect to zero-temperature freezing. Only at low connectivity do they remain trapped in a disordered configuration. Above a certain threshold, however, the zero-temperature dynamics quickly drives the model toward a broken symmetry (magnetized) state. Only above this threshold, which is almost twice as large as the percolation threshold, do we expect the Ising model to have a positive critical temperature. With a very good accuracy, the behavior on directed random graphs is reproduced within a certain approximate scheme.

Quantum turbulence in superfluids with wall-clamped normal component.

PubMed

Eltsov, Vladimir; Hänninen, Risto; Krusius, Matti

2014-03-25

In Fermi superfluids, such as superfluid (3)He, the viscous normal component can be considered to be stationary with respect to the container. The normal component interacts with the superfluid component via mutual friction, which damps the motion of quantized vortex lines and eventually couples the superfluid component to the container. With decreasing temperature and mutual friction, the internal dynamics of the superfluid component becomes more important compared with the damping and coupling effects from the normal component. As a result profound changes in superfluid dynamics are observed: the temperature-dependent transition from laminar to turbulent vortex motion and the decoupling from the reference frame of the container at even lower temperatures.

Single Particle Jumps in Sheared SiO2

NASA Astrophysics Data System (ADS)

McMahon, Sean; Vollmayr-Lee, Katharina; Cookmeyer, Jonathan; Horbach, Juergen

We study the dynamics of a sheared glass via molecular dynamics simulations. Using the BKS potential we simulate the strong glass former SiO2. The system is initially well equilibrated at a high temperature, then quenched to a temperature below the glass transition, and, after a waiting time at the desired low temperature, sheared with constant strain rate. We present preliminary results of an analysis of single particle trajectories of the sheared glass. We acknowledge the support via NSF REU Grant #PHY-1156964, DoD ASSURE program, and NSF-MRI CHE-1229354 as part of the MERCURY high-performance computer consortium. We thank G.P. Shrivastav, Ch. Scherer and B. Temelso.

Quantum turbulence in superfluids with wall-clamped normal component

PubMed Central

Eltsov, Vladimir; Hänninen, Risto; Krusius, Matti

2014-01-01

In Fermi superfluids, such as superfluid 3He, the viscous normal component can be considered to be stationary with respect to the container. The normal component interacts with the superfluid component via mutual friction, which damps the motion of quantized vortex lines and eventually couples the superfluid component to the container. With decreasing temperature and mutual friction, the internal dynamics of the superfluid component becomes more important compared with the damping and coupling effects from the normal component. As a result profound changes in superfluid dynamics are observed: the temperature-dependent transition from laminar to turbulent vortex motion and the decoupling from the reference frame of the container at even lower temperatures. PMID:24704879

Tuning the ferroelectric-to-paraelectric transition temperature and dipole orientation of group-IV monochalcogenide monolayers

NASA Astrophysics Data System (ADS)

Barraza-Lopez, Salvador; Kaloni, Thaneshwor P.; Poudel, Shiva P.; Kumar, Pradeep

2018-01-01

Coordination-related, two-dimensional (2D) structural phase transitions are a fascinating facet of two-dimensional materials with structural degeneracies. Nevertheless, a unified theoretical account of these transitions remains absent, and the following points are established through ab initio molecular dynamics and 2D discrete clock models here: Group-IV monochalcogenide (GeSe, SnSe, SnTe,...) monolayers have four degenerate structural ground states, and a phase transition from a threefold coordinated onto a fivefold coordinated structure takes place at finite temperature. On unstrained samples, this phase transition requires lattice parameters to evolve freely. A fundamental energy scale J permits understanding this transition, and numerical results indicate a transition temperature Tc of about 1.41 J . Numerical data provides a relation among the experimental (rhombic) parameter 〈Δ α 〉 [Chang et al., Science 353, 274 (2016), 10.1126/science.aad8609] and T of the form 〈Δ α 〉 =Δ α (T =0 ) (1-T /Tc)β , with a critical exponent β ≃1 /3 that coincides with experiment. It is also shown that 〈Δ α 〉 is temperature independent in another theoretical work [Fei et al., Phys. Rev. Lett. 117, 097601 (2016), 10.1103/PhysRevLett.117.097601], and thus incompatible with experiment. Tc and the orientation of the in-plane intrinsic electric dipole can be controlled by moderate uniaxial tensile strain, and a modified discrete clock model describes the transition on strained samples qualitatively. An analysis of out-of-plane fluctuations and a discussion of the need for van der Waals corrections to describe these materials are given too. These results provide an experimentally compatible framework to understand structural phase transitions in 2D materials and their effects on material properties.

Ultrafast structural and electronic dynamics of the metallic phase in a layered manganite

PubMed Central

Piazza, L.; Ma, C.; Yang, H. X.; Mann, A.; Zhu, Y.; Li, J. Q.; Carbone, F.

2013-01-01

The transition between different states in manganites can be driven by various external stimuli. Controlling these transitions with light opens the possibility to investigate the microscopic path through which they evolve. We performed femtosecond (fs) transmission electron microscopy on a bi-layered manganite to study its response to ultrafast photoexcitation. We show that a photoinduced temperature jump launches a pressure wave that provokes coherent oscillations of the lattice parameters, detected via ultrafast electron diffraction. Their impact on the electronic structure are monitored via ultrafast electron energy loss spectroscopy, revealing the dynamics of the different orbitals in response to specific structural distortions. PMID:26913564

Dynamics of asymmetric binary glass formers. I. A dielectric and nuclear magnetic resonance spectroscopy study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kahlau, R.; Bock, D.; Schmidtke, B.

2014-01-28

Dielectric spectroscopy as well as {sup 2}H and {sup 31}P nuclear magnetic resonance spectroscopy (NMR) are applied to probe the component dynamics of the binary glass former tripropyl phosphate (TPP)/polystyrene (PS/PS-d{sub 3}) in the full concentration (c{sub TPP}) range. In addition, depolarized light scattering and differential scanning calorimetry experiments are performed. Two glass transition temperatures are found: T{sub g1}(c{sub TPP}) reflects PS dynamics and shows a monotonic plasticizer effect, while the lower T{sub g2}(c{sub TPP}) exhibits a maximum and is attributed to (faster) TPP dynamics, occurring in a slowly moving or immobilized PS matrix. Dielectric spectroscopy probing solely TPP identifiesmore » two different time scales, which are attributed to two sub-ensembles. One of them, again, shows fast TPP dynamics (α{sub 2}-process), the other (α{sub 1}-process) displays time constants identical with those of the slow PS matrix. Upon heating the α{sub 1}-fraction of TPP decreases until above some temperature T{sub c} only a single α{sub 2}-population exists. Inversely, below T{sub c} a fraction of the TPP molecules is trapped by the PS matrix. At low c{sub TPP} the α{sub 2}-relaxation does not follow frequency-temperature superposition (FTS), instead it is governed by a temperature independent distribution of activation energies leading to correlation times which follow Arrhenius laws, i.e., the α{sub 2}-relaxation resembles a secondary process. Yet, {sup 31}P NMR demonstrates that it involves isotropic reorientations of TPP molecules within a slowly moving or rigid matrix of PS. At high c{sub TPP} the super-Arrhenius temperature dependence of τ{sub 2}(T), as well as FTS are recovered, known as typical of the glass transition in neat systems.« less

Inter- and intraplane softening of the vortex structure in Bi 2.1Sr 1.9Ca 0.9Cu 2O 8+δ: a two-step transition

NASA Astrophysics Data System (ADS)

Yazyi, J.; Arribére, A.; Durán, C.; de la Cruz, F.; Mitzi, D. B.; Kapitulnik, A.

1991-12-01

High Q mechanical oscillator and AC susceptibility techniques have been used to study vortex dynamics in high quality single crystals of Bi 2.1Sr 1.9Ca 0.9Cu 2O 8+δ over a wide range of magnetic fields and different relative orientations between the magnetic field and the crystalline c-axis. Our results confirm the existence of two transitions in the vortex response. We show that the transition at lower temperatures is associated to currents flowing across the Cu-O planes and the other one to currents in the planes. This means that the reversible region of the phase diagram is reached in two steps when increasing temperature.

Order-disorder phenomena in the low-temperature phase of BaTiO3

NASA Astrophysics Data System (ADS)

Völkel, G.; Müller, K. A.

2007-09-01

X - and Q -band electron paramagnetic resonance measurements are reported on Mn4+ -doped BaTiO3 single crystals in the rhombohedral low-temperature phase. The Mn4+ probe ion is statistically substitute for the isovalent Ti4+ ion. The critical line broadening observed when approaching the phase transition to the orthorhombic phase demonstrates the presence of order-disorder processes within the off-center Ti subsystem and the formation of dynamic precursor clusters with a structure compatible with one of the orthorhombic phase. From the data it is concluded that BaTiO3 shows a special type of phase transition where displacive and order-disorder character are not only present at the cubic-tetragonal transition, but also at the orthorhombic-rhombohedral transition at low temperatures. The disappearance of the Mn4+ spectrum in the orthorhombic, tetragonal, and cubic phases can be interpreted as the consequence of the strong line broadening caused by changes of the instantaneous off-center positions in time around the averaged off-center position along a body diagonal.

Effect of sugar addition on glass transition temperatures of cassava starch with low to intermediate moisture contents.

PubMed

Figueroa, Yetzury; Guevara, Marvilan; Pérez, Adriana; Cova, Aura; Sandoval, Aleida J; Müller, Alejandro J

2016-08-01

This work studies how sucrose (S) addition modifies the thermal properties of cassava starch (CS). Neat CS and CS-S blends with 4, 6 and 8% sugar contents (CS-S-4%, CS-S-6% and CS-S-8%) were prepared and analyzed by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA), in a wide range of moisture levels (2-20%). In equilibrated samples with moisture contents lower than 10%, twoendothermic steps were observed during first DSC heating scans and two corresponding relaxation maxima in tan δ were detected by DMTA. The first transition, detected at around 45-55°C by both DSC and DMTA, is frequently found in starchy foods, while the second observed at higher temperatures is associated to the glass transition temperature of the blends. At higher moisture contents, only one thermal transition was observed. Samples analyzed immediately after cooling from the melt (i.e., after erasing their thermal history), exhibited a single glass transition temperature, regardless of their moisture content. Addition of sugar promotes water plasticization of CS only at high moisture contents. In the low moisture content range, anti-plasticization was observed for both neat and sugar-added CS samples. Addition of sugar decreases the moisture content needed to achieve the maximum value of the glass transition temperature before plasticization starts. The results of this work may be valuable for the study of texture establishment in low moisture content extruded food products. Copyright © 2016 Elsevier Ltd. All rights reserved.

Temperature-Dependent Energy Gap Shift and Thermally Activated Transition in Multilayer CdTe/ZnTe Quantum Dots.

PubMed

Man, Minh Tan; Lee, Hong Seok

2015-10-01

We investigated the influence of growth conditions on carrier dynamics in multilayer CdTe/ZnTe quantum dots (QDs) by monitoring the temperature dependence of the photoluminescence emission energy. The results were analyzed using the empirical Varshni and O'Donnell relations for temperature variation of the energy gap shift. Best fit values showed that the thermally activated transition between two different states occurs due to band low-temperature quenching with values separated by 5.0-6.5 meV. The addition of stack periods in multilayer CdTe/ZnTe QDs plays an important role in the energy gap shift, where the exciton binding energy is enhanced, and, conversely, the exciton-phonon coupling strength is suppressed with an average energy of 19.3-19.8 meV.

Entropic Description of Gas Hydrate Ice-Liquid Equilibrium via Enhanced Sampling of Coexisting Phases

NASA Astrophysics Data System (ADS)

Małolepsza, Edyta; Kim, Jaegil; Keyes, Tom

2015-05-01

Metastable β ice holds small guest molecules in stable gas hydrates, so its solid-liquid equilibrium is of interest. However, aqueous crystal-liquid transitions are very difficult to simulate. A new molecular dynamics algorithm generates trajectories in a generalized N P T ensemble and equilibrates states of coexisting phases with a selectable enthalpy. With replicas spanning the range between β ice and liquid water, we find the statistical temperature from the enthalpy histograms and characterize the transition by the entropy, introducing a general computational procedure for first-order transitions.

Vibrational Relaxation and Dynamical Transitions in Atactic Polystyrene

NASA Astrophysics Data System (ADS)

Zhao, Hanqing; Park, Yung; Painter, Paul

2009-03-01

Infrared bands and Raman lines recorded in the frequency domain have a counterpart in the time domain in the form of time-correlation functions, which are sensitive to molecular dynamics on the picosecond time scale. This is explored by calculating time correlation functions and their variation with temperature for the conformationally insensitive modes observed near 1601 cm-1 and 1583 cm-1 in the infrared spectrum of atactic polystyrene. The correlation functions were modeled by assuming that there is a fast relaxation process characterized by a single relaxation time that is inhomogeneously broadened by a slower process, also characterized by a single relaxation time. The fundamental mode, near 1583 cm-1, is inhomogeneously broadened, but the relaxation time calculated for this mode is sensitive to temperature as a result of anharmonic coupling to a combination mode. A change in the modulation of the 1583 cm-1 band becomes apparent about 10--20 degrees below the thermally measured Tg. Relaxation times at first increase then decrease and becomes negligible at temperatures near 180 degrees. These results are consistent with theories of the glass transition.

A Ring Polymer Molecular Dynamics Approach to Study the Transition between Statistical and Direct Mechanisms in the H2 + H3+ → H3+ + H2 Reaction.

PubMed

Suleimanov, Yury V; Aguado, Alfredo; Gómez-Carrasco, Susana; Roncero, Octavio

2018-05-03

Because of its fundamental importance in astrochemistry, the H 2 + H 3 + → H 3 + + H 2 reaction has been studied experimentally in a wide temperature range. Theoretical studies of the title reaction significantly lag primarily because of the challenges associated with the proper treatment of the zero-point energy (ZPE). As a result, all previous theoretical estimates for the ratio between a direct proton-hop and indirect exchange (via the H 5 + complex) channels deviate from the experiment, in particular, at lower temperatures where the quantum effects dominate. In this work, the ring polymer molecular dynamics (RPMD) method is applied to study this reaction, providing very good agreement with the experiment. RPMD is immune to the shortcomings associated with the ZPE leakage and is able to describe the transition from direct to indirect mechanisms below room temperature. We argue that RPMD represents a useful tool for further studies of numerous ZPE-sensitive chemical reactions that are of high interest in astrochemistry.

Domain wall formation in late-time phase transitions

NASA Technical Reports Server (NTRS)

Kolb, Edward W.; Wang, Yun

1992-01-01

We examine domain wall formulation in late time phase transitions. We find that in the invisible axion domain wall phenomenon, thermal effects alone are insufficient to drive different parts of the disconnected vacuum manifold. This suggests that domain walls do not form unless either there is some supplemental (but perhaps not unreasonable) dynamics to localize the scalar field responsible for the phase transition to the low temperature maximum (to an extraordinary precision) before the onset of the phase transition, or there is some non-thermal mechanism to produce large fluctuations in the scalar field. The fact that domain wall production is not a robust prediction of late time transitions may suggest future directions in model building.

Quantum dynamics of thermalizing systems

NASA Astrophysics Data System (ADS)

White, Christopher David; Zaletel, Michael; Mong, Roger S. K.; Refael, Gil

2018-01-01

We introduce a method "DMT" for approximating density operators of 1D systems that, when combined with a standard framework for time evolution (TEBD), makes possible simulation of the dynamics of strongly thermalizing systems to arbitrary times. We demonstrate that the method performs well for both near-equilibrium initial states (Gibbs states with spatially varying temperatures) and far-from-equilibrium initial states, including quenches across phase transitions and pure states.

Anderson localization in sigma models

NASA Astrophysics Data System (ADS)

Bruckmann, Falk; Wellnhofer, Jacob

2018-03-01

In QCD above the chiral restoration temperature there exists an Anderson transition in the fermion spectrum from localized to delocalized modes. We investigate whether the same holds for nonlinear sigma models which share properties like dynamical mass generation and asymptotic freedom with QCD. In particular we study the spectra of fermions coupled to (quenched) CP(N-1) configurations at high temperatures. We compare results in two and three space-time dimensions: in two dimensions the Anderson transition is absent, since all fermion modes are localized, while in three dimensions it is present. Our measurements include a more recent observable characterizing level spacings: the distribution of ratios of consecutive level spacings.

Analog geometry in an expanding fluid from AdS/CFT perspective

NASA Astrophysics Data System (ADS)

Bilić, Neven; Domazet, Silvije; Tolić, Dijana

2015-04-01

The dynamics of an expanding hadron fluid at temperatures below the chiral transition is studied in the framework of AdS/CFT correspondence. We establish a correspondence between the asymptotic AdS geometry in the 4 + 1 dimensional bulk with the analog spacetime geometry on its 3 + 1 dimensional boundary with the background fluid undergoing a spherical Bjorken type expansion. The analog metric tensor on the boundary depends locally on the soft pion dispersion relation and the four-velocity of the fluid. The AdS/CFT correspondence provides a relation between the pion velocity and the critical temperature of the chiral phase transition.

Parallel replica dynamics with a heterogeneous distribution of barriers: Application to n-hexadecane pyrolysis

NASA Astrophysics Data System (ADS)

Kum, Oyeon; Dickson, Brad M.; Stuart, Steven J.; Uberuaga, Blas P.; Voter, Arthur F.

2004-11-01

Parallel replica dynamics simulation methods appropriate for the simulation of chemical reactions in molecular systems with many conformational degrees of freedom have been developed and applied to study the microsecond-scale pyrolysis of n-hexadecane in the temperature range of 2100-2500 K. The algorithm uses a transition detection scheme that is based on molecular topology, rather than energetic basins. This algorithm allows efficient parallelization of small systems even when using more processors than particles (in contrast to more traditional parallelization algorithms), and even when there are frequent conformational transitions (in contrast to previous implementations of the parallel replica algorithm). The parallel efficiency for pyrolysis initiation reactions was over 90% on 61 processors for this 50-atom system. The parallel replica dynamics technique results in reaction probabilities that are statistically indistinguishable from those obtained from direct molecular dynamics, under conditions where both are feasible, but allows simulations at temperatures as much as 1000 K lower than direct molecular dynamics simulations. The rate of initiation displayed Arrhenius behavior over the entire temperature range, with an activation energy and frequency factor of Ea=79.7 kcal/mol and log A/s-1=14.8, respectively, in reasonable agreement with experiment and empirical kinetic models. Several interesting unimolecular reaction mechanisms were observed in simulations of the chain propagation reactions above 2000 K, which are not included in most coarse-grained kinetic models. More studies are needed in order to determine whether these mechanisms are experimentally relevant, or specific to the potential energy surface used.

Discotic columnar liquid crystal studied in the bulk and nanoconfined states by molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Busselez, Rémi; Cerclier, Carole V.; Ndao, Makha; Ghoufi, Aziz; Lefort, Ronan; Morineau, Denis

2014-10-01

A prototypical Gay Berne discotic liquid crystal was studied by means of molecular dynamics simulations both in the bulk state and under confinement in a nanoporous channel. The phase behavior of the confined system strongly differs from its bulk counterpart: the bulk isotropic-to-columnar transition is replaced by a continuous ordering from a paranematic to a columnar phase. Moreover, a new transition is observed at a lower temperature in the confined state, which corresponds to a reorganization of the intercolumnar order. It reflects the competing effects of pore surface interaction and genuine hexagonal packing of the columns. The translational molecular dynamics in the different phases has been thoroughly studied and discussed in terms of collective relaxation modes, non-Gaussian behavior, and hopping processes.

Space-time thermodynamics of the glass transition

NASA Astrophysics Data System (ADS)

Merolle, Mauro; Garrahan, Juan P.; Chandler, David

2005-08-01

We consider the probability distribution for fluctuations in dynamical action and similar quantities related to dynamic heterogeneity. We argue that the so-called “glass transition” is a manifestation of low action tails in these distributions where the entropy of trajectory space is subextensive in time. These low action tails are a consequence of dynamic heterogeneity and an indication of phase coexistence in trajectory space. The glass transition, where the system falls out of equilibrium, is then an order-disorder phenomenon in space-time occurring at a temperature Tg, which is a weak function of measurement time. We illustrate our perspective ideas with facilitated lattice models and note how these ideas apply more generally. Author contributions: M.M., J.P.G., and D.C. performed research and wrote the paper.

Empirical temperature-dependent intermolecular potentials determined by data mining from crystal data

NASA Astrophysics Data System (ADS)

Hofmann, D. W. M.; Kuleshova, L. N.

2018-05-01

Modern force fields are accurate enough to describe thermal effects in molecular crystals. Here, we have extended our earlier approach to discrete force fields for various temperatures to a force field with a continuous function. For the parametrisation of the force field, we used data mining on experimental structures with the temperature as an additional descriptor. The obtained force field can be used to minimise energy at a finite temperature and for molecular dynamics with zero-K potentials. The applicability of the method has been demonstrated for the prediction of crystal density, temperature density gradients and transition temperature.

Correlating Free-Volume Hole Distribution to the Glass Transition Temperature of Epoxy Polymers.

PubMed

Aramoon, Amin; Breitzman, Timothy D; Woodward, Christopher; El-Awady, Jaafar A

2017-09-07

A new algorithm is developed to quantify the free-volume hole distribution and its evolution in coarse-grained molecular dynamics simulations of polymeric networks. This is achieved by analyzing the geometry of the network rather than a voxelized image of the structure to accurately and efficiently find and quantify free-volume hole distributions within large scale simulations of polymer networks. The free-volume holes are quantified by fitting the largest ellipsoids and spheres in the free-volumes between polymer chains. The free-volume hole distributions calculated from this algorithm are shown to be in excellent agreement with those measured from positron annihilation lifetime spectroscopy (PALS) experiments at different temperature and pressures. Based on the results predicted using this algorithm, an evolution model is proposed for the thermal behavior of an individual free-volume hole. This model is calibrated such that the average radius of free-volumes holes mimics the one predicted from the simulations. The model is then employed to predict the glass-transition temperature of epoxy polymers with different degrees of cross-linking and lengths of prepolymers. Comparison between the predicted glass-transition temperatures and those measured from simulations or experiments implies that this model is capable of successfully predicting the glass-transition temperature of the material using only a PDF of the initial free-volume holes radii of each microstructure. This provides an effective approach for the optimized design of polymeric systems on the basis of the glass-transition temperature, degree of cross-linking, and average length of prepolymers.

The use of inverse gas chromatography and gravimetric vapour sorption to study transitions in amorphous lactose.

PubMed

Ambarkhane, Ameet V; Pincott, Kim; Buckton, Graham

2005-04-27

The aim of this study was to measure the glass transition of amorphous lactose under well-controlled temperature and humidity, using inverse gas chromatography (IGC) and to relate these data to gravimetric vapour sorption experiments. Amorphous lactose (spray-dried) was exposed to a stepwise increment in the relative humidity (%RH) under isothermal conditions in an IGC. At the end of each conditioning step a decane injection was made, and the retention volumes were calculated using the maximum peak height (V(max)) method. The pressure drop across the column was recorded using the pressure transducers. These measurements were performed at various temperatures from 25 to 40 degrees C. The extent of water sorption at identical humidity (%RH) and temperature conditions was determined gravimetrically using dynamic vapour sorption (DVS). At each T, it was possible to determine: (1) a transition at low RH relating to the onset of mobility; (2) changes in retention volume relating to the point, where T(g) = T; (3) changes in pressure drop, which were related to the sample collapse. The rate and extent of water sorption was seen to alter at T(g) and also at a collapse point. Combinations of temperature and critical %RH (%cRH required to lower the dry glass transition temperature to the experimental temperature) obtained from IGC were comparable to those obtained from DVS. It was shown that at each T, the sample spontaneously crystallised, when T(g) was 32 degrees C below T. Inverse gas chromatograph can be used in this novel way to reveal the series of transitions that occur in amorphous materials.

Calorimetric and Neutron Scattering Studies on Glass Transitions and Ionic Diffusions in Imidazolium-based Ionic Liquids

NASA Astrophysics Data System (ADS)

Yamamuro, O.; Kofu, M.

2017-05-01

Glass transition is one of the central research issues of ionic liquids (ILs). In particular, the most typical ILs, imidazolium-basedones (ImILs) are readily supercooled and exhibit glass transitions below room temperature. We have measured the heat capacities of several ImILs, encoded as CnmimX (n: alkyl carbon number, n = 2-8, X: anion, X = Cl, I, FeCl4, TFSI) using an adiabatic calorimeter. We found that most of ImILs exhibit glass transitions with large Cp jumps in a temperature range between 170 K and 230 K. The large Cp jumps reflect that these ILs are fragile liquids that exhibit large structural change depending on temperature near the glass transition temperature T g. It is also revealed that T g does not depend much on n but on the anion radius. We have investigated the dynamics of CnmimX (n = 2-8, X = Cl, NO3, PF6, TF, FSI, TFSI) by means of a quasielastic neutron scattering (QENS) technique. It was clarified that the ionic diffusion is directly associated with the viscosity and glass transition. The activation energy ΔE a of the ionic diffusion increases with decreasing anion size but remains almost unchanged with n as found for T g. These systematic change of T g and ΔE a can be explained well by taking account the nano-domain structure which is the most characteristic feature of ImILs.

Stabilization of Model Membrane Systems by Disaccharides. Quasielastic Neutron Scattering Experiments and Atomistic Simulations

NASA Astrophysics Data System (ADS)

Doxastakis, Emmanouil; Garcia Sakai, Victoria; Ohtake, Satoshi; Maranas, Janna K.; de Pablo, Juan J.

2006-03-01

Trehalose, a disaccharide of glucose, is often used for the stabilization of cell membranes in the absence of water. This work studies the effects of trehalose on model membrane systems as they undergo a melting transition using a combination of experimental methods and atomistic molecular simulations. Quasielastic neutron scattering experiments on selectively deuterated samples provide the incoherent dynamic structure over a wide time range. Elastic scans probing the lipid tail dynamics display clear evidence of a main melting transition that is significantly lowered in the presence of trehalose. Lipid headgroup mobility is considerably restricted at high temperatures and directly associated with the dynamics of the sugar in the mixture. Molecular simulations provide a detailed overview of the dynamics and their spatial and time dependence. The combined simulation and experimental methodology offers a unique, molecular view of the physics of systems commonly employed in cryopreservation and lyophilization processes.

Formation of H2-He substellar bodies in cold conditions. Gravitational stability of binary mixtures in a phase transition

NASA Astrophysics Data System (ADS)

Füglistaler, A.; Pfenniger, D.

2016-06-01

Context. Molecular clouds typically consist of 3/4 H2, 1/4 He and traces of heavier elements. In an earlier work we showed that at very low temperatures and high densities, H2 can be in a phase transition leading to the formation of ice clumps as large as comets or even planets. However, He has very different chemical properties and no phase transition is expected before H2 in dense interstellar medium conditions. The gravitational stability of fluid mixtures has been studied before, but these studies did not include a phase transition. Aims: We study the gravitational stability of binary fluid mixtures with special emphasis on when one component is in a phase transition. The numerical results are aimed at applications in molecular cloud conditions, but the theoretical results are more general. Methods: First, we study the gravitational stability of van der Waals fluid mixtures using linearized analysis and examine virial equilibrium conditions using the Lennard-Jones intermolecular potential. Then, combining the Lennard-Jones and gravitational potentials, the non-linear dynamics of fluid mixtures are studied via computer simulations using the molecular dynamics code LAMMPS. Results: Along with the classical, ideal-gas Jeans instability criterion, a fluid mixture is always gravitationally unstable if it is in a phase transition because compression does not increase pressure. However, the condensed phase fraction increases. In unstable situations the species can separate: in some conditions He precipitates faster than H2, while in other conditions the converse occurs. Also, for an initial gas phase collapse the geometry is essential. Contrary to spherical or filamentary collapses, sheet-like collapses starting below 15 K easily reach H2 condensation conditions because then they are fastest and both the increase of heating and opacity are limited. Conclusions: Depending on density, temperature and mass, either rocky H2 planetoids, or gaseous He planetoids form. H2 planetoids are favoured by high density, low temperature and low mass, while He planetoids need more mass and can form at temperature well above the critical value.

Rationalizing the role of structural motif and underlying electronic structure in the finite temperature behavior of atomic clusters

NASA Astrophysics Data System (ADS)

Susan, Anju; Joshi, Kavita

2014-04-01

Melting in finite size systems is an interesting but complex phenomenon. Many factors affect melting and owing to their interdependencies it is a challenging task to rationalize their roles in the phase transition. In this work, we demonstrate how structural motif of the ground state influences melting transition in small clusters. Here, we report a case with clusters of aluminum and gallium having same number of atoms, valence electrons, and similar structural motif of the ground state but drastically different melting temperatures. We have employed Born-Oppenheimer molecular dynamics to simulate the solid-like to liquid-like transition in these clusters. Our simulations have reproduced the experimental trends fairly well. Further, the detailed analysis of isomers has brought out the role of the ground state structure and underlying electronic structure in the finite temperature behavior of these clusters. For both clusters, isomers accessible before cluster melts have striking similarities and does have strong influence of the structural motif of the ground state. Further, the shape of the heat capacity curve is similar in both the cases but the transition is more spread over for Al36 which is consistent with the observed isomerization pattern. Our simulations also suggest a way to characterize transition region on the basis of accessibility of the ground state at a specific temperature.

Transient transition from free carrier metallic state to exciton insulating state in GaAs by ultrafast photoexcitation

NASA Astrophysics Data System (ADS)

Nie, X. C.; Song, Hai-Ying; Zhang, Xiu; Gu, Peng; Liu, Shi-Bing; Li, Fan; Meng, Jian-Qiao; Duan, Yu-Xia; Liu, H. Y.

2018-03-01

We present systematic studies of the transient dynamics of GaAs by ultrafast time-resolved reflectivity. In photoexcited non-equilibrium states, we found a sign reverse in reflectivity change ΔR/R, from positive around room temperature to negative at cryogenic temperatures. The former corresponds to a free carrier metallic state, while the latter is attributed to an exciton insulating state, in which the transient electronic properties is mostly dominated by excitons, resulting in a transient metal–insulator transition (MIT). Two transition temperatures (T 1 and T 2) are well identified by analyzing the intensity change of the transient reflectivity. We found that photoexcited MIT starts emerging at T 1 as high as ∼ 230 K, in terms of a dip feature at 0.4 ps, and becomes stabilized below T 2 that is up to ∼ 180 K, associated with a negative constant after 40 ps. Our results address a phase diagram that provides a framework for the inducing of MIT through temperature and photoexcitation, and may shed light on the understanding of light-semiconductor interaction and exciton physics.

Kinetics of temperature response of PEO-b-PNIPAM-b-PAA triblock terpolymer aggregates and of their complexes with lysozyme

DOE PAGES

Papagiannopoulos, Aristeidis; Meristoudi, Anastasia; Hong, Kunlun; ...

2015-12-18

We present the kinetics of temperature response of a PEO-b-PNIPAM-b-PAA triblock terpolymer and of its complexes with lysozyme in aqueous solution. It is found that during the coil-to-globule transition of PNIPAM new bonds within the polymer aggregates are created, making the transition of the aggregates partially irreversible. This effect is also found for the protein loaded PEO-b-PNIPAM-b-PAA aggregates whereas in this case protein globules appear to enhance the formation of bonds, making the transition totally irreversible. The internal dynamics of both aggregates and complexes are “frozen” once the temperature is increased upon PINIPAM's LCST in water and remain so evenmore » when the temperature drops below LCST. As a result, we investigate the complexation kinetics of lysozyme and PEO-b-PNIPAM-b-PAA and observe that it occurs in two stages, one where protein globules adsorb on single pre-formed aggregates and one where protein globules cause inter-aggregate clustering.« less

A theory for the atmospheric energy spectrum: depth-limited temperature anomalies at the tropopause.

PubMed

Tulloch, R; Smith, K S

2006-10-03

The horizontal spectra of atmospheric wind and temperature at the tropopause have a steep -3 slope at synoptic scales, but transition to -5/3 at wavelengths of the order of 500-1,000 km [Nastrom, G. D. & Gage, K. S. (1985) J. Atmos. Sci. 42, 950-960]. Here we demonstrate that a model that assumes zero potential vorticity and constant stratification N over a finite-depth H in the troposphere exhibits the same type of spectra. In this model, temperature perturbations generated at the planetary scale excite a direct cascade of energy with a slope of -3 at large scales, -5/3 at small scales, and a transition near horizontal wavenumber k(t) = f/NH, where f is the Coriolis parameter. Ballpark atmospheric estimates for N, f, and H give a transition wavenumber near that observed, and numerical simulations of the previously undescribed model verify the expected behavior. Despite its simplicity, the model is consistent with a number of perplexing features in the observations and demonstrates that a complete theory for mesoscale dynamics must take temperature advection at boundaries into account.

Kinetics of temperature response of PEO-b-PNIPAM-b-PAA triblock terpolymer aggregates and of their complexes with lysozyme

DOE Office of Scientific and Technical Information (OSTI.GOV)

Papagiannopoulos, Aristeidis; Meristoudi, Anastasia; Hong, Kunlun

We present the kinetics of temperature response of a PEO-b-PNIPAM-b-PAA triblock terpolymer and of its complexes with lysozyme in aqueous solution. It is found that during the coil-to-globule transition of PNIPAM new bonds within the polymer aggregates are created, making the transition of the aggregates partially irreversible. This effect is also found for the protein loaded PEO-b-PNIPAM-b-PAA aggregates whereas in this case protein globules appear to enhance the formation of bonds, making the transition totally irreversible. The internal dynamics of both aggregates and complexes are “frozen” once the temperature is increased upon PINIPAM's LCST in water and remain so evenmore » when the temperature drops below LCST. As a result, we investigate the complexation kinetics of lysozyme and PEO-b-PNIPAM-b-PAA and observe that it occurs in two stages, one where protein globules adsorb on single pre-formed aggregates and one where protein globules cause inter-aggregate clustering.« less

Phase ordering in disordered and inhomogeneous systems

NASA Astrophysics Data System (ADS)

Corberi, Federico; Zannetti, Marco; Lippiello, Eugenio; Burioni, Raffaella; Vezzani, Alessandro

2015-06-01

We study numerically the coarsening dynamics of the Ising model on a regular lattice with random bonds and on deterministic fractal substrates. We propose a unifying interpretation of the phase-ordering processes based on two classes of dynamical behaviors characterized by different growth laws of the ordered domain size, namely logarithmic or power law, respectively. It is conjectured that the interplay between these dynamical classes is regulated by the same topological feature that governs the presence or the absence of a finite-temperature phase transition.