Ultraslow Dynamics Research Articles

Ultraslow Dynamics at a Charged Silicon–Ionic Liquid Interface Revealed by X-ray Reflectivity

The interfacial structure of the room temperature ionic liquid methyltrioctylammonium bis(trifluoromethylsulfonyl)imide ([MTOA]+[NTF2]−) near a silicon electrode was investigated using specular X-ray reflectivity. Using this technique, we have previously observed “crowding”, i.e., formation of a thick anion layer on a positively charged electrode. We now report that this layer develops over time scales in the range ∼400–1100 s. This is different from the time scales reported in other experiments, and is inconsistent with most theoretical predictions. A tentative explanation is proposed which assumes that the formation and dispersion of the crowding layer requires collective reordering of anions/cations through the electrochemical cell. We suggest that because of the presence of multiple time scales in these systems, the observed time scales will vary depending on the time scale of the measurement.

Evolution of Hot Polaron States with a Nanosecond Lifetime in a Manganite Perovskite

Understanding and controlling the relaxation process of optically excited charge carriers in solids with strong correlations is of great interest in the quest for new strategies to exploit solar energy. Usually, optically excited electrons in a solid thermalize rapidly on a femtosecond to picosecond timescale due to interactions with other electrons and phonons. New mechanisms to slow down thermalization will thus be of great significance for efficient light energy conversion, e.g., in photovoltaic devices. Ultrafast optical pump–probe experiments in the manganite Pr0.65Ca0.35MnO3, a photovoltaic, thermoelectric, and electrocatalytic material with strong polaronic correlations, reveal an ultraslow recombination dynamics on a nanosecond‐time scale. The nature of long living excitations is further elucidated by photovoltaic measurements, showing the presence of photodiffusion of excited electron–hole polaron pairs. Theoretical considerations suggest that the excited charge carriers are trapped in a hot polaron state. Escape from this state is possible via a slow dipole‐forbidden recombination process or via rare thermal fluctuations toward a conical intersection followed by a radiation‐less decay. The strong correlation between the excited polaron and the octahedral dynamics of its environment appears to be substantial for stabilizing the hot polaron.

Ultraslow Dynamics of a Framework Linker in MIL-53 (Al) as a Sensor for Different Isomers of Xylene

MIL-53 (Al) is an important example of metal–organic frameworks (MOFs) with a flexible framework capable to efficiently separate ortho and para isomers of xylene at moderate temperatures. The MIL-53 MOF contains mobile terephthalate phenylene fragments that can be used as a dynamic probe to investigate the guest–host interactions and the origin of the separation selectivity. Here 2H NMR spin alignment echo technique for the first time was applied to probe ultraslow structural mobility (0.1–1 kHz) in MOFs materials, with particular application to MIL-53(Al) saturated with ortho or para isomers of xylene. A specific influence of different isomers of xylene adsorbed in the MOF pores on the rotation of the phenylenes in MIL-53 for the temperature range with proved separation selectivity (T < 393 K) is shown. It has been established that the rotation of phenylene fragments is sensitive to the type of xylene isomer. The phenylenes’ rotation performs 1 order of magnitude slower in the presence of o-xylene (korth...

Dysregulation of Prefrontal Cortex-Mediated Slow-Evolving Limbic Dynamics Drives Stress-Induced Emotional Pathology

Circuits distributed across cortico-limbic brain regions compose the networks that mediate emotional behavior. The prefrontal cortex (PFC) regulates ultraslow (<1Hz) dynamics across these networks, and PFC dysfunction is implicated in stress-related illnesses including major depressive disorder (MDD). To uncover the mechanism whereby stress-induced changes in PFC circuitry alter emotional networks to yield pathology, we used a multi-disciplinary approach including invivo recordings in mice and chronic social defeat stress. Our network model, inferred using machine learning, linked stress-induced behavioral pathology to the capacity of PFC to synchronize amygdala and VTA activity. Direct stimulation of PFC-amygdala circuitry with DREADDs normalized PFC-dependent limbic synchrony in stress-susceptible animals and restored normal behavior. In addition to providing insights into MDD mechanisms, our findings demonstrate an interdisciplinary approach that can be used to identify the large-scale network changes that underlie complex emotional pathologies and the specific network nodes that can be used to develop targeted interventions.

Dynamic regional phase synchrony (DRePS): An Instantaneous Measure of Local fMRI Connectivity Within Spatially Clustered Brain Areas.

Dynamic functional brain connectivity analysis is a fast expanding field in computational neuroscience research with the promise of elucidating brain network interactions. Sliding temporal window based approaches are commonly used in order to explore dynamic behavior of brain networks in task-free functional magnetic resonance imaging (fMRI) data. However, the low effective temporal resolution of sliding window methods fail to capture the full dynamics of brain activity at each time point. These also require subjective decisions regarding window size and window overlap. In this study, we introduce dynamic regional phase synchrony (DRePS), a novel analysis approach that measures mean local instantaneous phase coherence within adjacent fMRI voxels. We evaluate the DRePS framework on simulated data showing that the proposed measure is able to estimate synchrony at higher temporal resolution than sliding windows of local connectivity. We applied DRePS analysis to task-free fMRI data of 20 control subjects, revealing ultra-slow dynamics of local connectivity in different brain areas. Spatial clustering based on the DRePS feature time series reveals biologically congruent local phase synchrony networks (LPSNs). Taken together, our results demonstrate three main findings. Firstly, DRePS has increased temporal sensitivity compared to sliding window correlation analysis in capturing locally synchronous events. Secondly, DRePS of task-free fMRI reveals ultra-slow fluctuations of ∼0.002-0.02 Hz. Lastly, LPSNs provide plausible spatial information about time-varying brain local phase synchrony. With the DRePS method, we introduce a framework for interrogating brain local connectivity, which can potentially provide biomarkers of human brain function in health and disease. Hum Brain Mapp 37:1970-1985, 2016. © 2016 Wiley Periodicals, Inc.

Water modulates the ultraslow dynamics of hydrated ionic liquids near CG rich DNA: consequences for DNA stability.

Ionic liquids are known to stabilize DNA for much longer than water can. While the source of this stability has commonly been attributed to thermodynamic aspects, we probe the dynamical aspects of the ionic liquids near DNA to further our understanding of this stability. Using molecular dynamics simulation, we calculated the mean residence time (MRT) of the cations of five different ionic liquids (ILs) in the grooves and around phosphate groups of AT and CG rich DNA segments. We find the residence time of different cations next to CG rich DNA to be much higher compared to that next to AT rich DNA, with a negligible difference with the variation of anions. The interaction energy between cations and DNA, however, shows exactly the opposite trend; it is much lower (indicating a stronger interaction) for AT than for CG. Investigation of DNA parameters reveals an insignificant difference for the DNA sequences under consideration. Analysis of water behavior provides a rationale for the long MRTs of cations; water molecules have been found to be denser and to possess higher MRT when next to CG-rich DNA, thus resulting in a crowded environment. Our results indicate that the dynamics influence the binding of ILs to different DNA sequences, possibly by modulating the entropy of the binding process.

Severe slowing-down and universality of the dynamics in disordered interacting many-body systems: ageing and ultraslow diffusion

Low-dimensional, many-body systems are often characterized by ultraslow dynamics. We study a labelled particle in a generic system of identical particles with hard-core interactions in a strongly disordered environment. The disorder is manifested through intermittent motion with scale-free sticking times at the single particle level. While for a non-interacting particle we find anomalous diffusion of the power-law form of the mean squared displacement with , we demonstrate here that the combination of the disordered environment with the many-body interactions leads to an ultraslow, logarithmic dynamics with a universal exponent. Even when a characteristic sticking time exists but the fluctuations of sticking times diverge we observe the mean squared displacement with , that is slower than the famed Harris law without disorder. We rationalize the results in terms of a subordination to a counting process, in which each transition is dominated by the forward waiting time of an ageing continuous time process.

A carrier relaxation bottleneck probed in single InGaAs quantum dots using integrated superconducting single photon detectors

Using integrated superconducting single photon detectors, we probe ultra-slow exciton capture and relaxation dynamics in single self-assembled InGaAs quantum dots embedded in a GaAs ridge waveguide. Time-resolved luminescence measurements performed with on- and off-chip detection reveal a continuous decrease in the carrier relaxation time from 1.22 ± 0.07 ns to 0.10 ± 0.07 ns upon increasing the number of non-resonantly injected carriers. By comparing off-chip time-resolved spectroscopy with spectrally integrated on-chip measurements, we identify the observed dynamics in the rise time (τr) as arising from a relaxation bottleneck at low excitation levels. From the comparison with the temporal dynamics of the single exciton transition with the on-chip emission signal, we conclude that the relaxation bottleneck is circumvented by the presence of charge carriers occupying states in the bulk material and the two-dimensional wetting layer continuum. A characteristic τr ∝ P−2∕3 power law dependence is observed suggesting Auger-type scattering between carriers trapped in the quantum dot and the two-dimensional wetting layer continuum which circumvents the phonon relaxation bottleneck.

Ultraslow Dynamics of Water in Organic Molecular Solids

The relaxation dynamics of water in hygroscopic molecular solids is probed by broadband dielectric spectroscopy in the temperature range from 200 to 450 K. Evidence is found for three types of dynamic processes. The intermediate process is common to all probed materials and is associated with the reorientation of bound water molecules that are attached directly onto organic molecules and counterions. A faster process is observed in rhodamine chloride and fullerol, which is the dynamic signature of water in higher hydration layers, either at grain boundaries (rhodamine) or in interstitial clusters (fullerol). All these processes are observed near room temperature and exhibit nonmonotonic temperature dependence and decreasing spectral strength upon heating. In fullerol a third, ultraslow relaxation is observed at high temperature, which may be due to the reorientation of water–fullerol complexes or to the diffusion of water vapor through intermolecular voids.

Ultra-slow dynamics in low density amorphous ice revealed by deuteron NMR: indication of a glass transition

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.

Random Fields at a Nonequilibrium Phase Transition

We study nonequilibrium phase transitions in the presence of disorder that locally breaks the symmetry between two equivalent macroscopic states. In low-dimensional equilibrium systems, such random-field disorder is known to have dramatic effects: it prevents spontaneous symmetry breaking and completely destroys the phase transition. In contrast, we show that the phase transition of the one-dimensional generalized contact process persists in the presence of random-field disorder. The ultraslow dynamics in the symmetry-broken phase is described by a Sinai walk of the domain walls between two different absorbing states. We discuss the generality and limitations of our theory, and we illustrate our results by large-scale Monte Carlo simulations.

Unreachable glass transition in dilute dipolar magnet

In magnetic systems the combined effects of disorder and frustration may cause the moments to freeze into a disordered state at a spin-glass transition. Recent experiments have shown that the rare earth compound LiHo(0.045)Y(0.955)F(4) freezes, but that the transition is unreachable because of dynamics that are 10(7) times slower than in ordinary spin-glass materials. This conclusion refutes earlier investigations reporting a speed-up of the dynamics into an exotic anti-glass phase caused by entanglement of quantum dipoles. Here we present a theory, backed by numerical simulations, which describes the material in terms of classical dipoles governed by Glauber dynamics. The dipoles freeze and we find that the ultra-slow dynamics are caused by rare, strongly ordered clusters, which give rise to a previously predicted, but hitherto unobserved, Griffths phase between the paramagnetic and spin-glass phases. In addition, the hyperfine interaction creates a high energy barrier to flipping the electronic spin, resulting in a clear signature in the dynamic correlation function.

Temperature Dependence of Multilayering at the Free Surface of Ionic Liquids Probed by X-ray Reflectivity Measurements

The effect of the temperature on the surface layering of ionic liquids has been studied for two ionic liquids, trioctylmethylammonium bis(nonafluorobutanesulfonyl)amide([TOMA(+)][C(4)C(4)N(-)]) and trihexyltetradecylphosphonium bis(nonafluorobutanesulfonyl)amide ([THTDP(+)][C(4)C(4)N(-)]), using X-ray reflectivity measurements at 285, 300, and 315 K. Both [TOMA(+)][C(4)C(4)N(-)] and [THTDP(+)][C(4)C(4)N(-)] develop multilayers at the surface. The structure of the multilayers at the [TOMA(+)][C(4)C(4)N(-)] surface shows little temperature-dependent change, whereas that at the [THTDP(+)][C(4)C(4)N(-)] surface clearly becomes diffused with increasing temperature. The different temperature dependence seems to be related to the difference in the recently reported ultraslow dynamics of the interfacial structure of [TOMA(+)][C(4)C(4)N(-)] and [THTDP(+)][C(4)C(4)N(-)] at the ionic liquid|water interface.

Voltammetric Manifestation of the Ultraslow Dynamics at the Interface between Water and an Ionic Liquid

The ultraslow relaxation (on the order of minutes) of the electrical double-layer structure, related to a change in the phase-boundary potential across the interface between water (W) and the ionic liquid (IL) trioctylmethylammonium bis(nonafluorobutanesufonyl)amide ([TOMA(+)][C(4)C(4)N(-)]) (Y. Yasui et al., J. Phys. Chem. B. 2009, 113, 3273), appears to be invisible in the transfer of tetrapropylammonium ions across the [TOMA(+)][C(4)C(4)N(-)]|W interface, provided that the charging current, which shows an unusual dependence on the voltage scan rate, is subtracted to obtain the faradaic current. This counterintuitive observation can be explained by the differences in the timescales of the fast and slow components of the relaxation dynamics of the electrical double layer on the IL side (ms and min). In contrast, the effect of the slow dynamics becomes surfaced in ion-transfer voltammetry when the ion is surface-active. The transfer of pentadecafluorooctanoate across the [TOMA(+)][C(4)C(4)N(-)]|W interface is irreversible, which is attributable to the self-inhibition of pentadecafluorooctanoate ions transferred to the IL phase. This process is likely to be affected by the ultraslow structural change of the IL side of the interface.

Ultraslow quantum dynamics in a sub-Ohmic heat bath

We show that the low-frequency modes of a sub-Ohmic bosonic heat bath generate an effective dynamical asymmetry for an intrinsically symmetric quantum spin -1/2. An initially fully polarized spin first decays towards a quasiequilibrium determined by the dynamical asymmetry, thereby showing coherent damped oscillations on the (fast) time scale of the spin splitting. On top of this, the dynamical asymmetry itself decays on an ultraslow time scale and vanishes asymptotically since the global equilibrium phase is symmetric. We quantitatively study the nature of the initial fast decay to the quasiequilibrium and discuss the features of ultraslow dynamics of the quasiequilibrium itself. The dynamical asymmetry is more pronounced for smaller values of the sub-Ohmic exponent and for lower temperatures, which emphasizes the quantum many-body nature of the effect. The symmetry breaking is related to the dynamic crossover between coherent and overdamped relaxation of the spin polarization and is not connected to the localization quantum phase transition. In addition to this delocalized phase, we identify a novel phase which is characterized by damped coherent oscillations in the localized phase. This allows for a sketch of the zero-temperature phase diagram of the sub-Ohmic spin-boson model with four distinct phases.

Slow Debye-type peak observed in the dielectric response of polyalcohols

Dielectric relaxation spectroscopy of glass forming liquids normally exhibits a relaxation scenario that seems to be surprisingly general. However, the relaxation dynamics is more complicated for hydrogen bonded liquids. For instance, the dielectric response of monoalcohols is dominated by a mysterious Debye-like process at lower frequencies than the structural alpha-relaxation that is normally dominating the spectra of glass formers. For polyalcohols this process has been thought to be absent or possibly obscured by a strong contribution from conductivity and polarization effects at low frequencies. We here show that the Debye-like process, although much less prominent, is also present in the response of polyalcohols. It can be observed in the derivative of the real part of the susceptibility or directly in the imaginary part if the conductivity contribution is reduced by covering the upper electrode with a thin Teflon layer. We report on results from broadband dielectric spectroscopy studies of several polyalcohols: glycerol, xylitol, and sorbitol. The findings are discussed in relation to other experimental observations of ultraslow (i.e., slower than the viscosity related alpha-relaxation) dynamics in glass formers.

The future of photo-induced phase transition (PIPT) – How fast and slow it can be changed?

The study of photo-controled nature of materials, including their optical, magnetic, and conducting properties, is a fascinating research field. The finding of photo-induced phase transition (PIPT) has triggered the search for inorganic and organic systems with highly efficient and ultrafast photo-responses. As a result of the recent progress in quantum-beam technologies, the time-resolved study of PIPT dynamics on the femto-second time scale, which is comparable with the single-cycle of phonon vibration, has become feasible. In contrast, ultra-slow dynamics on the time scales of a few seconds to several minutes play an important role in the cooperative phenomena in complex systems. Here, we review both the ultra-fast and ultra-slow dynamics of the photo-induced cooperative effects in a typical organic CT crystal (EDO-TTF)2PF6 and a protein molecule, myoglobin (Mb). In the case of Mb, we discuss the results from the viewpoint of a unique photo-functionality, i.e., the photo-induced transportation of a small molecule in the "super-structure" of a protein molecule.

Direct-space investigation of the ultraslow ballistic dynamics of a soft glass

We use light microscopy to investigate the aging dynamics of a glass made of closely packed soft spheres, following a rapid transition from a fluid to a solidlike state. By measuring time-resolved, coarse-grained displacement fields, we identify two classes of dynamical events, corresponding to reversible and irreversible rearrangements, respectively. The reversible events are due to the small, experimentally unavoidable fluctuations of the temperature imposed to the sample, leading to transient thermal expansions and contractions that cause shear deformations. The irreversible events are plastic rearrangements, induced by the repeated shear cycles. We show that the displacement due to the irreversible rearrangements grows linearly with time, both on average and at a local level. The velocity associated with this ballistic motion decreases exponentially with sample age, accounting for the observed slowing down of the dynamics. The displacement field due to the irreversible rearrangements has a vortexlike structure and is spatially correlated over surprisingly long distances.

Exploring the Picosecond Time Domain of the Solvation Dynamics of Coumarin 153 within β-Cyclodextrins

We report molecular dynamics simulation results of equilibrium and dynamical characteristics pertaining to the solvation of the dye coumarin 153 (C153) trapped within hydrophobic cavities of di- and trimethylated beta-cyclodextrins (CD) in aqueous solutions. We found that stable configurations of the encapsulated probe are characterized by a slanted docking, in which the plane of the C153 lies mostly parallel to one of the glucose units of the CD. "In and out" dynamical modes of the encapsulated probe present very small amplitudes. The rotational dynamics of the trapped coumarin can be cast in terms of a simple model that includes diffusive motions within a local restrictive environment coupled to the overall rotational motion of the CD. We have examined the early stages of the solvation response of the environment following a vertical excitation of the probe. Regardless of the degree of CD methylation, the water dynamical response seems to be completed within 2-3 ps and does not differ substantially from that observed for nonencapsulated probes. The CD response is characterized by a single, subpicosecond relaxation that involves intramolecular motions. We also explored dynamical modes that could account for the recently reported persistence of Stokes shifts in the nanosecond time domain. In all cases, the only sources of ultraslow dynamics that we detected were those associated with gauche-trans interconversions in primary hydroxyl chains of the CD, which do not seem to be directly connected to the electronic excitation of the probe.

The emergence of network communities by the action of coevolving market agents

The agent-based multileader model of the stock price dynamics on the directed evolving complex network is studied by direct simulation. The resulting stationary regime follows from the balance of extremal dynamics, adaptivity of the strategic variables, and reconnection rules. For given parametric combination, the network displays small-world phenomenon with high clustering coefficients and power-law node degree distribution. The fitness exploration by the mechanism of repeated random walk is used to violate dominance of centralized leadership. The simulation suggests that ultra slow dynamics of fitness implies explanation of the long-time volatility of the log-price returns.