The diffusion and relaxation of Gaussian chains in narrow rectangular slits

The confinement of a polymer to volumes whose characteristic linear dimensions are comparable to or smaller than its bulk radius of gyration R-G,R-bulk can produce significant changes in its static and dynamic properties, with important implications for the understanding of single-molecule processes in biology and chemistry. In this paper, we present calculations of the effects of a narrow rectangular slit of thickness d on the scaling behavior of the diffusivity D and relaxation time tau(r) of a Gaussian chain of polymerization index N and persistence length l(0). The calculations are based on the Rouse-Zimm model of chain dynamics, with the pre-averaged hydrodynamic interaction being obtained from the solutions to Stokes equations for an incompressible fluid in a parallel plate geometry in the limit of small d. They go beyond de Gennes' purely phenomenological analysis of the problem based on blobs, which has so far been the only analytical route to the determination of chain scaling behavior for this particular geometry. The present model predicts that D similar to dN(-1) ln(N/d(2)) and tau(r) similar to N(2)d(-1) ln(N/d(2))(-1) in the regime of moderate confinement, where l(0) << d < R-G,R-bulk. The corresponding results for the blob model have exactly the same power law behavior, but contain no logarithmic corrections; the difference suggests that segments within a blob may actually be partially draining and not non-draining as generally assumed. (C) 2013 AIP Publishing LLC.

Rapid, microwave-assisted synthesis of Gd2O3 and Eu:Gd2O3 nanocrystals: characterization, magnetic, optical and biological studies

Ultra-small crystals of undoped and Eu-doped gadolinium oxide (Gd2O3) were synthesised by a simple, rapid microwave-assisted route, using benzyl alcohol as the reaction solvent. XRD, XPS and TEM analysis reveal that the as-prepared powder material consists of nearly monodisperse Gd2O3 nanocrystals with an average diameter of 5.2 nm. The nanocrystals show good magnetic behaviour and exhibit a larger reduction in relaxation time of water protons than the standard Gd-DTPA complex currently used in MRI imaging. Cytotoxicity studies (both concentration- and time-dependent) of the Gd2O3 nanocrystals show no adverse effect on cell viability, evidencing their high biological compatibility. Finally, Eu:Gd2O3 nanocrystals were prepared by a similar route and the red luminescence of Eu3+ activator ions was used to study the cell permeability of the nanocrystals. Red fluorescence from Eu3+ ions observed by fluorescence microscopy shows that the nanocrystals (Gd2O3 and Eu:Gd2O3) can permeate not only the cell membrane but can also enter the cell nucleus, rendering them candidate materials not only for MRI imaging but also for drug delivery when tagged or functionalized with specific drug molecules.

A Comparison of Machine Learning Techniques for Modeling River Flow Time Series: The Case of Upper Cauvery River Basin

Models of river flow time series are essential in efficient management of a river basin. It helps policy makers in developing efficient water utilization strategies to maximize the utility of scarce water resource. Time series analysis has been used extensively for modeling river flow data. The use of machine learning techniques such as support-vector regression and neural network models is gaining increasing popularity. In this paper we compare the performance of these techniques by applying it to a long-term time-series data of the inflows into the Krishnaraja Sagar reservoir (KRS) from three tributaries of the river Cauvery. In this study flow data over a period of 30 years from three different observation points established in upper Cauvery river sub-basin is analyzed to estimate their contribution to KRS. Specifically, ANN model uses a multi-layer feed forward network trained with a back-propagation algorithm and support vector regression with epsilon intensive-loss function is used. Auto-regressive moving average models are also applied to the same data. The performance of different techniques is compared using performance metrics such as root mean squared error (RMSE), correlation, normalized root mean squared error (NRMSE) and Nash-Sutcliffe Efficiency (NSE).

Investigation of dielectric relaxation, Jahn-Teller distortion, and magnetic ordering in Y substituted Pr1-xYxMnO3 (0.1 <= x <= 0.4)

We report structural, magnetic, and dielectric properties of the perovskite compound Pr1-xYxMnO3 (0.1 <= x <= 0.4) studied using dc magnetization, ac susceptibility, neutron powder diffraction, and dielectric techniques. These compounds crystallize in orthorhombic space group (Pnma) in the temperature range 5-300 K. The Mn-O-Mn bond angle decreases with the Y substitution along with an increase in the Jahn-Teller distortion. The Jahn-Teller distortion for Pr0.9Y0.1MnO3 shows an anomalous change near 50 K, below which it falls sharply. Neutron powder diffraction patterns of all reported compositions at low temperature constitute additional magnetic Bragg peaks that suggest magnetic ordering. Magnetic reflections were indexed in the nuclear lattice with the propagation vector k = (0, 0, 0). Rietveld refinement of powder patterns conform to A type antiferromagnetic ordering where moments are aligned ferromagnetically in a-c plane and coupled nearly antiferromagnetically along b-axis resulting in a net ferromagnetic component along the b-direction. The antiferromagnetic transition temperature was deduced from dc magnetization and ac susceptibility data. The transition temperature decreases by nearly 22 K (from 81 K to 59 K) as yttrium content (x) increases from 0.1 to 0.4. Measurements reveal strong frequency dispersion in dielectric constant and dielectric loss. Activation energy and relaxation time are estimated from the Arrhenius plot. It is further shown that relaxation behaviour is altered with yttrium doping concentration. (C) 2015 AIP Publishing LLC.

Probing Photoexcited Carriers in a Few-Layer MoS2 Laminate by Time-Resolved Optical Pump-Terahertz Probe Spectroscopy

We report the dynamics of photoinduced carriers in a free-standing MoS2 laminate consisting of a few layers (1-6 layers) using time-resolved optical pump-terahertz probe spectroscopy. Upon photoexcitation with the 800 nm pump pulse, the terahertz conductivity increases due to absorption by the photoinduced charge carriers. The relaxation of the non-equilibrium carriers shows fast as well as slow decay channels, analyzed using a rate equation model incorporating defect-assisted Auger scattering of photoexcited electrons, holes, and excitons. The fast relaxation time occurs due to the capture of electrons and holes by defects via Auger processes, resulting in nonradiative recombination. The slower relaxation arises since the excitons are bound to the defects, preventing the defect-assisted Auger recombination of the electrons and the holes. Our results provide a comprehensive understanding of the non-equilibrium carrier kinetics in a system of unscreened Coulomb interactions, where defect-assisted Auger processes dominate and should be applicable to other 2D systems.

Gradient echo single scan inversion recovery: application to proton and fluorine relaxation studies

Single scan longitudinal relaxation measurement experiments enable rapid estimation of the spin-lattice relaxation time (T-1) as the time series of spin relaxation is encoded spatially in the sample at different slices resulting in an order of magnitude saving in time. We consider here a single scan inversion recovery pulse sequence that incorporates a gradient echo sequence. The proposed pulse sequence provides spectra with significantly enhanced signal to noise ratio leading to an accurate estimation of T-1 values. The method is applicable for measuring a range of T-1 values, thus indicating the possibility of routine use of the method for several systems. A comparative study of different single scan methods currently available is presented, and the advantage of the proposed sequence is highlighted. The possibility of the use of the method for the study of cross-correlation effects for the case of fluorine in a single shot is also demonstrated. Copyright (C) 2015 John Wiley & Sons, Ltd.

Gradient echo single scan inversion recovery: application to proton and fluorine relaxation studies

Single scan longitudinal relaxation measurement experiments enable rapid estimation of the spin-lattice relaxation time (T-1) as the time series of spin relaxation is encoded spatially in the sample at different slices resulting in an order of magnitude saving in time. We consider here a single scan inversion recovery pulse sequence that incorporates a gradient echo sequence. The proposed pulse sequence provides spectra with significantly enhanced signal to noise ratio leading to an accurate estimation of T-1 values. The method is applicable for measuring a range of T-1 values, thus indicating the possibility of routine use of the method for several systems. A comparative study of different single scan methods currently available is presented, and the advantage of the proposed sequence is highlighted. The possibility of the use of the method for the study of cross-correlation effects for the case of fluorine in a single shot is also demonstrated. Copyright (C) 2015 John Wiley & Sons, Ltd.

“Deborah Numbers”, Coupling Multiple Space and Time Scales and Governing Damage Evolution to Failure

Two different spatial levels are involved concerning damage accumulation to eventual failure. nucleation and growth rates of microdamage nN* and V*. It is found that the trans-scale length ratio c*/L does not directly affect the process. Instead, two independent dimensionless numbers: the trans-scale one * * ( V*)including the * **5 * N c V including mesoscopic parameters only, play the key role in the process of damage accumulation to failure. The above implies that there are three time scales involved in the process: the macroscopic imposed time scale tim = /a and two meso-scopic time scales, nucleation and growth of damage, (* *4) N N t =1 n c and tV=c*/V*. Clearly, the dimensionless number De*=tV/tim refers to the ratio of microdamage growth time scale over the macroscopically imposed time scale. So, analogous to the definition of Deborah number as the ratio of relaxation time over external one in rheology. Let De be the imposed Deborah number while De represents the competition and coupling between the microdamage growth and the macroscopically imposed wave loading. In stress-wave induced tensile failure (spallation) De* < 1, this means that microdamage has enough time to grow during the macroscopic wave loading. Thus, the microdamage growth appears to be the predominate mechanism governing the failure. Moreover, the dimensionless number D* = tV/tN characterizes the ratio of two intrinsic mesoscopic time scales: growth over nucleation. Similarly let D be the “intrinsic Deborah number”. Both time scales are relevant to intrinsic relaxation rather than imposed one. Furthermore, the intrinsic Deborah number D* implies a certain characteristic damage. In particular, it is derived that D* is a proper indicator of macroscopic critical damage to damage localization, like D* ∼ (10–3~10–2) in spallation. More importantly, we found that this small intrinsic Deborah number D* indicates the energy partition of microdamage dissipation over bulk plastic work. This explains why spallation can not be formulated by macroscopic energy criterion and must be treated by multi-scale analysis.

I. Spectroscopic evidence for slow vibrational relaxation in excited electronic states of diatomics in rare gas solids. II. Static crystal field effects in the electronic spectra of isotopically mixed benzene crystals

Part I

Studies of vibrational relaxation in excited electronic states of simple diatomic molecules trapped in solid rare-gas matrices at low temperatures are reported. The relaxation is investigated by monitoring the emission intensity from vibrational levels of the excited electronic state to vibrational levels of the ground electronic state. The emission was in all cases excited by bombardment of the doped rare-gas solid with X-rays.

The diatomics studied and the band systems seen are: N₂, Vegard-Kaplan and Second Positive systems; O₂, Herzberg system; OH and OD, A ²Σ⁺ - X²II_i system. The latter has been investigated only in solid Ne, where both emission and absorption spectra were recorded; observed fine structure has been partly interpreted in terms of slightly perturbed rotational motion in the solid. For N₂, OH, and OD emission occurred from v' > 0, establishing a vibrational relaxation time in the excited electronic state of the order, of longer than, the electronic radiative lifetime. The relative emission intensity and decay times for different v' progressions in the Vegard-Kaplan system are found to depend on the rare-gas host and the N₂ concentration, but are independent of temperature in the range 1.7°K to 30°K.

Part II

Static crystal field effects on the absorption, fluorescence, and phosphorescence spectra of isotopically mixed benzene crystals were investigated. Evidence is presented which demonstrate that in the crystal the ground, lowest excited singlet, and lowest triplet states of the guest deviate from hexagonal symmetry. The deviation appears largest in the lowest triplet state and may be due to an intrinsic instability of the ³B_1u state. High resolution absorption and phospho- rescence spectra are reported and analyzed in terms of site-splitting of degenerate vibrations and orientational effects. The guest phosphorescence lifetime for various benzene isotopes in C₆D₆ and sym-C₆H₃D₃ hosts is presented and discussed.

Mössbauer effect investigations of the hyperfine interactions and relaxation phenomena in salts of thulium

Two new phenomena have been observed in Mössbauer spectra: a temperature-dependent shift of the center of gravity of the spectrum, and an asymmetric broadening of the spectrum peaks. Both phenomena were observed in thulium salts. In the temperature range 1˚K ≤ T ≤ 5˚K the observed shift has an approximate inverse temperature dependence. We explain this on the basis of a Van Vleck type of interaction between the magnetic moment of two nearly degenerate electronic levels and the magnetic moment of the nucleus. From the size of the shift we are able to deduce an “effective magnetic field” H = (6.0 ± 0.1) x 10⁶ Gauss, which is proportional to ‹r^-3›_M‹G|J|E› where ‹r^-3›_M is an effective magnetic radial integral for the 4f electrons and |G› and |E› are the lowest 4f electronic states in Tm Cl₃·6H₂O. From the temperature dependence of the shift we have derived a preliminary value of 1 cm^-1 for the splitting of these two states. The observed asymmetric line broadening is independent of temperature in the range 1˚K ≤ T ≤ 5˚K, but is dependent on the concentration of thulium ions in the crystal. We explain this broadening on the basis of spin-spin interactions between thulium ions. From size and concentration dependence of the broadening we are able to deduce a spin-spin relaxation time for Tm Cl₃·6H₂O of the order of 10^-11 sec.

90° domain dynamics and relaxation in thin ferroelectric/ferroelastic films

We investigated the dynamics and relaxation of 90° domains in 60-nm-thick lead-zirconium titanate (PbZr0.3 T0.7 O3) films, with enhanced piezoresponse force microscopy. We show that under opposite electric fie ld, ferroelectric domains are reversibly switched while ferroelastic domains reorganize in a nonreversible way. Moreover, we show that the relaxation-time constant of 90° domains is two orders of magnitude shorter than for the previously reported 180° domains relaxation. Furthermore, we demonstrate the influence of geometry and scale on the relaxation process. Finally, we propose a relaxation mechanism for ferroelastic-ferroelectric systems, with implications for devices based on these materials. © 2010 The American Physical Society.

Temperature dependence of hole spin relaxation in ultrathin InAs monolayers

The temperature dependence of hole spin relaxation time in both neutral and n-doped ultrathin InAs monolayers has been investigated. It has been suggested that D'yakonov-Perel (DP) mechanism dominates the spin relaxation process at both low and high temperature regimes. The appearance of a peak in temperature dependent spin relaxation time reveals the important contribution of Coulomb scatterings between carriers to the spin kinetics at low temperature, though electron-phonon scattering becomes dominant at higher temperatures. Increased electron screening effect in the n-doped sample has been suggested to account for the shortened spin relaxation time compared with the undoped one. The results suggest that hole spins are also promising for building solid-state qubits.

Localized and free exciton spin relaxation dynamics in GaInNAs/GaAs quantum well

We have investigated the exciton spin relaxation in a GaInNAs/GaAs quantum well. The recombination from free and localized excitons is resolved on the basis of an analysis of the photoluminescence characteristics. The free exciton spin relaxation time is measured to be 192 ps at 10 K, while the localized exciton spin relaxation time is one order of magnitude longer than that of the free exciton. The dependence of the free exciton spin relaxation time on the temperature above 50 K suggests that both the D'yakonov-Perel' and the Elliot-Yafet effects dominate the spin relaxation process. The temperature independence below 50 K is considered to be due to the spin exchange interaction. The ultralong spin relaxation time of the localized excitons is explained to be due to the influence of nonradiative deep centers. (c) 2008 American Institute of Physics.

Spin relaxation in submonolayer and monolayer InAs structures grown in a GaAs matrix

Electron-spin dynamics in InAs/GaAs heterostructures consisting of a single layer of InAs (1/3-1 monolayer) embedded in (001) and (311)A GaAs matrix was studied by means of time-resolved Kerr rotation spectroscopy. The spin-relaxation time of the submonolayer InAs samples is significantly enhanced, compared with that of the monolayer InAs sample. The electron-spin-relaxation time and the effective g factor in submonolayer samples were found to be strongly dependent on the photogenerated carrier density. The contribution from both the D'yakonov-Perel' mechanism and Bir-Aronov-Pikus mechanism are discussed to interpret the temperature dependence of spin decoherence at various carrier densities.

Hole Spin Relaxation in an Ultrathin InAs Monolayer

We investigate the spin relaxation time of holes in an ultrathin neutral InAs monolayer (1.5 ML) and compare with that of electrons, using polarization-dependent time-resolved photoluminescence (TRPL) experiments. With excitation energies above the GaAs gap, we observe a rather slow relaxation of holes (tau(1h) = 196 +/- 17 ps) that is in the magnitude similar to electrons (tau(1e) = 354 +/- 32 ps) in this ultrathin sample. The results are in good agreement with earlier theoretical prediction, and the phonon scattering due to spin-orbit coupling is realized to play a dominant role in the carrier spin kinetics.