Compressed-exponential relaxations in supercooled liquid trehalose

We investigated the α-relaxations in supercooled liquid trehalose by using photon correlation spectroscopy (PCS) and found an interesting compressed-exponential relaxation at temperatures above 140 °C. The q^?1 dependence of its relaxation time corresponds to an ultraslow ballistic motion due to the local structure rearrangements. In the same temperature range, we found the glycosidic bond structure changes in trehalose molecule from the Raman scattering and the X-ray direction measurements. We concluded that the compressed-exponential relaxation in supercooled liquid trehalose might originate from the intra-molecular (glycosidic bond) structure change.     

Relaxation processes in supercooled confined water and implications for protein dynamics

We show that the viscosity-related main (alpha) relaxation of confined water vanishes at a temperature where the volume required for the cooperative alpha relaxation becomes larger than the size of the geometrically confined water cluster. This occurs typically around 200 K, implying that above this temperature we observe a merged alpha-beta relaxation, whereas below it only a local (beta) relaxation remains. This also means that such confined supercooled water does not exhibit any true glass transition, in contrast to other liquids in similar confinements. Furthermore, it implies that deeply supercooled water in biological systems, such as membranes and proteins, generally shows only a local beta relaxation, a finding of importance for low temperature properties of biological materials.     

Correlation of primary and secondary relaxations in a supercooled liquid

The widespread assumption that primary and secondary relaxations in glass-forming materials are independent processes is scrutinized using spin-lattice relaxation weighted stimulated-echo spectroscopy. This nuclear magnetic resonance (NMR) technique is simultaneously sensitive to the dynamics on well-separated time scales. For the deeply supercooled liquid sorbitol, which exhibits a strong secondary relaxation, the primary relaxation (that is observable using NMR) can be modified by suppressing the contributions of those subensembles which are characterized by relatively slow secondary relaxations. This is clear evidence for a correlation between primary and secondary relaxation times. In the disordered crystal orthocarborane high-frequency processes are absent and consequently no such modifications could be achieved.     

室温下(Ga,Mn)As中载流子的自旋弛豫特性

运用飞秒时间分辨抽运-探测克尔光谱技术,研究了室温下退火及未退火(Ga,Mn)As的载流子自旋弛豫的激发能量密度依赖性,发现电子自旋弛豫时间随激发能量密度增加而增大,而在同一激发能量密度下,退火样品比未退火样品具有更短的载流子复合时间、电子自旋弛豫时间和更大的克尔转角,显示DP机理是室温下(Ga,Mn)As的电子自旋弛豫的主导机理.退火(Ga,Mn)As的超快克尔增强效应显示其在超高速全光自旋开关方面的潜在应用价值,也为(Ga,Mn)As铁磁性起源的p-d交换机理提供了证据. 关键词： (Ga Mn)As稀磁半导体 时间分辨克尔光谱 电子自旋弛豫 DP机理     

Experimental observation of the alpha relaxation in supercooled water

Intermediate scattering functions for density fluctuation in D2O contained in pores of a Vycor glass have been measured using an improved neutron spin-echo spectrometer at two supercooled temperatures. The measurements cover the time range from 1 to 2300 ps with the Q range spanning the first diffraction peak of water. The time correlation functions can be fitted to a stretched exponential relaxation function with a Q-dependent amplitude. Both the stretch exponent and the relaxation time peak approximately at the Q value corresponding to the first diffraction peak, confirming the validity of the mode coupling idea in supercooled water.     

Does confined water exhibit a fragile-to-strong transition?

The dynamics of supercooled confined water has recently been shown to have a pronounced, apparent fragile-to-strong transition (FST). Here we use broadband dielectric spectroscopy (10^-2–10⁹ Hz) to study the dynamics of water confined in silica matrices MCM-41 C10 and C18, with pore diameter of 21.4 and 36.1 ?, respectively. The local dynamics of water molecules and the dynamics of the hydroxyl groups on the inner wall of the pores are followed up to over 240 K. We argue that the reported FST for confined water is due to the vanishing of the cooperative α relaxation, which implies that it should not be interpreted as a true FST.     

Rotational dynamics of Di-tert-butyl-nitroxide in normal and supercooled water: an electron paramagnetic resonance study

In order to obtain dynamical information on the water solvent, which is characterized by a strong anomalous behavior in its structural and transport properties especially in the supercooled region, low concentration di-tert-butyl-nitroxide (DTBN) aqueous solutions were studied by Electron Paramagnetic Resonance spectroscopy in the temperature range from 28 down to ?17°C. The accurate spectra reconstruction, achieved by a multi-parameters Monte Carlo fitting algorithm, allowed us to reliably extract some relevant spectral parameters of the spin probe, which were connected to the probe dynamics in the framework of the motional narrowing magnetic relaxation theory. The observed trend with the temperature showed however a significant deviation from what expected from the magnetic relaxation model. This anomalous behavior is discussed in terms of the influence upon the probe motion of solvent-induced local fluctuating structures which, very likely, are connected to the water hydrogen bond network dynamics.     

Analysis of inelastic x-ray scattering spectra of low-temperature water

We analyze a set of high-resolution inelastic x-ray scattering (IXS) spectra from H2O measured at T=259, 273, and 294 K using two different phenomenological models. Model I, called the "dynamic cage model," combines the short time in-cage dynamics described by a generalized Enskog kinetic theory with a long-time cage relaxation dynamics described by an alpha relaxation. This model is appropriate for supercooled water where the cage effect is dominant and the existence of an alpha relaxation is evident from molecular-dynamics (MD) simulation data of extended simple point charge (SPC/E) model water. Model II is essentially a generalized hydrodynamic theory called the "three effective eigenmode theory" by de Schepper et al. 11. This model is appropriate for normal liquid water where the cage effect is less prominent and there is no evidence of the alpha relaxation from the MD data. We use the model I to analyze IXS data at T=259 K (supercooled water). We successfully extract the Debye-Waller factor, the cage relaxation time from the long-time dynamics, and the dispersion relation of high-frequency sound from the short time dynamics. We then use the model II to analyze IXS data at all three temperatures, from which we are able to extract the relaxation rate of the central mode and the damping of the sound mode as well as the dispersion relation for the high-frequency sound. It turns out that the dispersion relations extracted from the two models at their respective temperatures agree with each other giving the high-frequency sound speed of 2900+/-300 m/s. This is to be compared with a slightly higher value reported previously, 3200+/-320 m/s, by analyzing similar IXS data with a phenomenological-damped harmonic oscillator model 22. This latter model has traditionally been used exclusively for the analysis of inelastic scattering spectra of water. The k-dependent sound damping and central mode relaxation rate extracted from our model analyses are compared with the known values in the hydrodynamic limit.     

Chain-length-dependent relaxation scenarios in an oligomeric glass-forming system: from merged to well-separated alpha and beta loss peaks

We have studied the relaxation dynamics of a homologous series of propylene glycol based dimethyl ethers in the supercooled regime by means of broadband dielectric spectroscopy. The system is chosen in order to minimize changes of the intermolecular interactions with varying molecular weight, M. A gradual transformation from a scenario of well-separated to one of merged alpha and beta loss peaks was observed with decreasing M. The results give strong evidence for the currently debated excess wing being due to an underlying beta relaxation. The study suggests that the main difference between glass formers with and without excess wings is the relaxation time at the merging temperature.     

Supercooled confined water and the mode coupling crossover temperature

We present a molecular dynamics study of the single-particle dynamics of supercooled water confined in a silica pore. Two dynamical regimes are found. Close to the hydrophilic substrate molecules are below the mode coupling crossover temperature, T(C), already at ambient temperature. The water closer to the center of the pore (free water) approaches upon supercooling T(C) as predicted by mode coupling theories. For free water the crossover temperature and crossover exponent gamma are extracted from power-law fits to both the diffusion coefficient and the relaxation time of the late alpha region.     

Light-scattering study of a supercooled epoxy resin

The dynamics of the fragile glass-forming liquid diglycidyl ether of bisphenol-A was studied by depolarized Rayleigh-Brillouin light-scattering and photon correlation spectroscopy above the glass transition, in the temperature range from 261 to 473 K and in the frequency range from 1 Hz to 300 GHz. The structural (alpha-) relaxation process was revealed and no signature of the secondary relaxation previously evidenced by dielectric spectroscopy at about 0.1 GHz was observed. The characteristic time of the alpha process differs from that determined by dielectric spectroscopy of an amount, which increases with increasing temperature. The relaxation times were compared with viscosity data to test the predictions of the classic Stokes-Einstein-Debye model. The tau proportional, variant eta behavior was verified for dielectric data, while a fractional power law of viscosity tau proportional, variant eta(0.89) was obtained for light-scattering relaxation times, extending over more than seven decades in viscosity and time. This deviation of light scattering from viscosity data could be interpreted in terms of cooperative motion in the supercooled liquid with a characteristic length xi(a) proportional, variant(T-T0)(-v) where T(0)=229 K is the Vogel temperature and v is close to 2 / 3 which is consistent with the prediction of the fluctuation theory of glass transition.     

Glassy dynamics

We review dynamic processes in supercooled liquids and glasses as studied by dielectric spectroscopy. It is the only experimental technique which allows one to follow the tremendous slow-down of diffusive motion of particles in disordered condensed matter over more than 18 decades in frequency or time. The dielectric techniques used are treated in detail. As an introduction for non-specialists, the time and temperature evolution of the basic spectral features associated with various dynamic relaxation processes are discussed in detail. Among them are the structural relaxation, the occurrence of fast processes and the boson peak. The relevance of these features for glass formation is discussed. The present article may also serve as a review for recent experimental and theoretical studies on glass-forming liquids.     

Nonlinear viscoelastic dynamics of nanoconfined wetting liquids

The viscoelastic dynamics of nanoconfined wetting liquids is studied by means of atomic force microscopy. We observe a nonlinear viscoelastic behavior remarkably similar to that widely observed in metastable complex fluids. We show that the origin of the measured nonlinear viscoelasticity in nanoconfined water and silicon oil is a strain rate dependent relaxation time and slow dynamics. By measuring the viscoelastic modulus at different frequencies and strains, we find that the intrinsic relaxation time of nanoconfined water is in the range 0.1-0.0001 s, orders of magnitude longer than that of bulk water, and comparable to the dielectric relaxation time measured in supercooled water at 170-210 K.     

界面生长中断对GaAs (111)衬底上 AlGaAs/GaAs量子阱电子自旋寿命的影响

用固源分子束外延技术(SSMBE)在GaAs(111)衬底上,采用不同的界面中断时间生长了多组AlGaAs/GaAs多量子阱样品(MQWs),通过室温发光光谱和时间分辨克尔旋转谱(TRKR)研究了界面生长中断对发光光谱半峰全宽(FWHM)和量子阱中电子自旋弛豫时间(自旋寿命)的影响,发现了自旋寿命随着界面生长中断时间的增加呈现先减小后增加的趋势,此变化趋势与荧光光谱半峰全宽表征的材料质量随中断时间的变化一致,适当的界面生长中断时间能有效的增加GaAs (111)衬底上AlGaAs/GaAs 多量子阱中电子自旋寿命。     

Effect of electron-hole spatial correlation on spin relaxation dynamics in InAs submonolayer

Using time-resolved photoluminescence and time-resolved Kerr rotation spectroscopy, we explore the unique electron spin behavior in an InAs submonolayer sandwiched in a GaAs matrix, which shows very different spin characteristics under resonant and non-resonant excitations. While a very long spin relaxation lifetime of a few nanoseconds at low temperature is observed under non-resonant excitation, it decreases dramatically under resonant excitation. These interesting results are attributed to the difference in electron-hole interactions caused by non-geminate or geminate capture of photo-generated electron-hole pairs in the two excitation cases, and provide a direct verification of the electron-hole spatial correlation effect on electron spin relaxation.     

Anomalous electrical conductivity behavior at elevated pressure in the protic ionic liquid procainamide hydrochloride

Using broadband dielectric spectroscopy, we investigated the effect of hydrostatic pressure on the conductivity relaxation time τ{σ} of the supercooled protic ionic liquid, procainamide hydrochloride, a common pharmaceutical. The pressure dependence of τ{σ} exhibited anomalous behavior in the vicinity of the glass transition T{g}, manifested by abrupt changes in activation volume. This peculiar behavior, paralleling the change in temperature dependence of τ{σ} near T{g}, is a manifestation of the decoupling between electrical conductivity and structural relaxation. Although the latter effectively ceases in the glassy state, free ions retain their mobility but with a reduced sensitivity to thermodynamic changes. This is the first observation of decoupling of ion migration from structural relaxation in a glassy conductor by isothermal densification.     

Microscopic dynamics of recovery in sheared depletion gels

We report x-ray photon correlation spectroscopy and diffusing wave spectroscopy studies of depletion gels formed from nanoscale silica colloids in solutions of nonabsorbing polymer following the cessation of shear. The two techniques provide a quantitatively coherent picture of the dynamics as ballistic or convective motion of colloidal clusters whose internal motion is arrested. While the dynamics possesses features characteristic of nonergodic soft solids, including a relaxation time that grows linearly with the time since shear, comparison with behavior of quenched supercooled liquids indicates that this evolution is not directly related to traditional aging phenomena in glasses.     

Optical studies of spin precession in magnetic two-dimensional electron gases

Magnetic two-dimensional electron gases are studied using time-resolved Kerr and Faraday rotation spectroscopy in the Voigt geometry. The data directly reveal both electron and Mn spin precession in modest transverse fields. Scattering by Mn ions dominates the electron spin relaxation processes in these materials, and prevents the electron gas from acquiring a long-lived spin polarization as observed in non-magnetic structures. Nonetheless, a persistent Mn spin polarization occurs which creates a oscillating magnetic field within the electron gas for hundreds of picoseconds.     

Spatiotemporal instability in dispersive nonlinear Kerr medium with a finite response time

We investigated the spatiotemporal modulation instability (MI) in a medium with a non-instantaneous Kerr response in which the nonlinear contribution to the refractive index is governed by a relaxing Debye type equation. The expression for the MI gain spectrum in non-instantaneous Kerr medium is obtained, which clearly reveals the influence of the finite time of the nonlinear response (relaxation effect) on the spatiotemporal MI. It is shown that, due to the relaxation effect, the spatiotemporal MI can appear for the case of anomalous dispersion and defocusing nonlinearity, while it cannot appear in instantaneous Kerr medium for the same case, and a new MI gain spectrum appears, adding to the conventional MI gain spectrum similar to that in an instantaneous Ker medium. In addition, the bandwidth of MI gain spectrum is extended and the maximum MI gain is reduced with increasing of the relaxation time. Interestingly, spatiotemporal MI can appear for any spatial frequencies in non-instantaneous Kerr medium for any combination of dispersion and nonlinearity. We have performed an experiment of MI in carbon disulfide (CS₂), a typical non-instantaneous Kerr medium, which shows quantitative agreement with the theoretical analyses.