Local Relaxation Research Articles

Universal Structural Influence on the 2D Electron Gas at SrTiO3 Surfaces.

The 2‐dimensional electron gas (2DEG) found at the surface of SrTiO3 and related interfaces has attracted significant attention as a promising basis for oxide electronics. In order to utilize its full potential, the response of this 2DEG to structural changes and surface modification must be understood in detail. Here, a study of the detailed electronic structure evolution of the 2DEG as a function of sample temperature and surface step density is presented. By comparing the experimental results with ab initio calculations, it is shown that local structure relaxations cause a metal‐insulator transition of the system around 135 K. This study presents a new and simple way of tuning the 2DEG via surface vicinality and identifies how the operation of prospective devices will respond to changes in temperature.

Local structure, glass transition, structural relaxation, and crystallization of functional oxide glasses investigated by Mössbauer spectroscopy and DTA

Local structure, glass transition, structural relaxation, and crystallization of functional oxide glasses investigated by Mössbauer spectroscopy and DTA

Dynamical response of localized electron hopping and dipole relaxation in Cu1 − x Zn x Fe2O4 magnetoceramics

We report a detailed study on the dynamical response of localized electron hopping and dipole relaxation in bulk polycrystals of Zn diluted Cuprospinel (Cu1 − x Zn x Fe2O4). The variations in the dielectric dispersion and ac-resistivity (ρ ac ) were analyzed over a wide temperature (77 K ≤T ≤ 823 K) and frequency (20 Hz ≤ f ≤ 20 MHz) window for a critical composition x c = 0.4. The variation of R (f, T) followed the Maxwell–Wagner type polarization mechanism in-line with the Koops phenomenological theory. Our analysis of ρ ac (T, f) provide strong evidence to the Mott’s variable range hopping of charge transport between the localized states at low temperatures, however, thermally-activated Arrhenius like behaviour was noticed at high temperatures with E A = 656 meV for x c = 0.4. Moreover, electric modulus spectroscopic studies (M *(f, T)) reveals two distinct types of relaxation phenomena: (i) the short-range oscillations of the charge carriers within the potential well of grains and (ii) the long-range movement of charge carriers across the grain boundaries. The depressed semi-circles of the Nyquist plots and lower values of non-exponential parameter extracted from M *(f, T) suggest the non-Debye type relaxation process present in the system with a widespread distribution of relaxation times. The frequency exponent (s(x, T)) study of Jonscher’s power law reveals that the ac-conductivity follows small-polaron tunnelling followed by the correlated-barrier-hopping mechanism for 0.1. However, for x ≥ x c reorientational hopping mechanism is predominant, except for 400 K, where thermally activated Arrhenius-type conduction of charge carriers is prevalent in this spinel system. Furthermore, the tetragonally (I41/amd) distorted systems (x ≤ 0.05) exhibit less activation energy (E A − VRH ) values as compared to those of cubic-spinel symmetry (Fd-3m) which saturates at 130 meV for 0.1 ≤ x ≤ 0.6. Compositional dependent tunability of the above discussed parameters may open a constructive approach to design low energy-loss and high-resistive electromagnetic elements for microwave devices which is the key significance of the present study.

An all-Mach, low-dissipation strategy for simulating multiphase flows

Liquid-gas flows that involve compressibility effects occur in many engineering contexts, and high-fidelity simulations can unlock further insights and developments. Introducing several numerical innovations, this work details a collocated, volume-of-fluid, finite volume flow solver that is robust, conservative, and capable of simulating flows with shocks, liquid-gas interfaces, and turbulence. A novel hybrid advection scheme provides stability while minimizing dissipation. An unsplit semi-Lagrangian method provides the robustness and precision to handle discontinuities in the flow, and a centered scheme eliminates numerical kinetic energy dissipation elsewhere, allowing accurate simulation of turbulence. A pressure projection scheme makes multiphase compressible simulations much less costly, and formulating this projection as incremental reduces numerical dissipation further. Local relaxation to mechanical equilibrium is used to properly solve for the pressure and energy fields in multiphase contexts. Within this framework, a consistent methodology for implementing multiphase pressure projection is derived, including surface tension. The complete algorithm is validated with benchmark tests in one, two, and three dimensions that evaluate the accuracy and stability of the approach in predicting compressible effects, turbulent dissipation, interface dynamics, and more through comparisons with theory, experiments, and reference simulations. Finally, the utility of the numerical approach is demonstrated by simulating an atomizing liquid jet in a Mach 2 crossflow.

Relaxation transitions and compatibility of binary blended PVDF/PVB systems

In this paper we investigated local molecular dynamics and relaxation transitions of PVDF/PVB blended systems with different compositions. The temperatures of relaxation transitions of these systems were determined by the conformationally-inhomogeneous probes method and compared with that for pure PVDF and PVB. The relaxation transitions in the blended systems under investigation were assigned to the types of local molecular mobility of polymer chains. It was shown that PVDF/PVB blended systems were fully compatible when PVB content was not above 40%. The degree of crystallinity of PVDF/PVB blended systems was determined by FTIR spectra.

Fastest Local Entanglement Scrambler, Multistage Thermalization, and a Non-Hermitian Phantom

We study random quantum circuits and their rate of producing bipartite entanglement, specifically with respect to the choice of 2-qubit gates and the order (protocol) in which these are applied. The problem is mapped to a Markovian process and proved that there are large spectral equivalence classes -- different configurations have the same spectrum. Optimal gates and the protocol that generate entanglement with the fastest theoretically possible rate are identified. Relaxation towards the asymptotic thermal entanglement proceeds via a series of phase transitions in the local relaxation rate, which is a consequence of non-Hermiticity. In particular, non-Hermiticity can cause the rate to be either faster, or, even more interestingly, slower than predicted by the matrix eigenvalue gap. This is caused by an exponential in system size explosion of expansion coefficient sizes resulting in a 'phantom' eigenvalue, and is due to non-orthogonality of non-Hermitian eigenvectors. We numerically demonstrate that the phenomenon occurs also in random circuits with non-optimal generic gates, random U(4) gates, and also without spatial or temporal randomness, suggesting that it could be of wide importance also in other non-Hermitian settings, including correlations.

Stress-Strain and Stress-Relaxation Behaviors of Solution-Coated Layers Composed of Block Copolymers Mixed with Tackifiers.

The relationship between the mechanical properties and the structure of block copolymers mixed with tackifiers whose relative solubility to the respective components of block copolymers differs was examined. Coated layers were prepared by solution coating using a block copolymer composed of polystyrene (PS) and polyisoprene (PI), which forms spherical microdomains of PS in the PI matrix, mixed with three types of tackifiers: aliphatic (C5) resin, aliphatic–aromatic (C5–C9) resin, and rosin ester (RE) resin. Furthermore, the correlation between the changes in the nanostructure and mechanical properties including the stress-relaxation behaviors was clarified by two-dimensional small-angle X-ray scattering measurement. The amount of the PI-bridge conformation in the case of C5 resin is the lowest, resulting in the lowest stress. On the contrary, the largest amount of RE resin was solubilized in the PS phase so that it can be considered that pulling out of the PS chains took place easily. We were able to explain the stress-relaxation behavior by fitting with the three-component exponent functions. The triple exponential decay functions indicate the hierarchy of the structures that are the origins of the ″fast mode″ relating to the local relaxation due to the rotation of the repeating unit of polymer chains; the ″intermediate mode″ of the disentanglement of the mid-PI chains; and the ″slow mode″ relating to, in this particular case, pulling out of the PS chains from the PS sphere.

Spin-wave localization and guiding by magnon band structure engineering in yttrium iron garnet

In spintronics, the propagation of spin-wave excitations in magnetically ordered materials can also be used to transport and process information. One of the most popular materials in this regard is the ferrimagnetic insulator yttrium iron garnet due its exceptionally small spin-wave damping parameter. While the small relaxation rate allows for large propagation length of magnetic excitations, it also leads to nonlocality of the magnetic properties. By imaging spin waves, their band structure is mapped with high-frequency resolution using a magneto-optic super-Nyquist sampling technique. In doing so, wave-vector selection is shown to suppress dispersion effects to a large extent, allowing for local measurements of spin relaxation. Moreover, we demonstrate even higher control of magnon propagation by employing the wave-vector selectivity near an avoided crossing of different spin-wave modes where the group velocity approaches zero. Here the local engineering of the dispersion allows us to construct magnonic waveguides, and at the same time it reveals the local relaxation properties.

Dielectric properties of A-site Mn-doped bismuth sodium titanate perovskite: (Bi0·5Na0.5)0.9Mn0·1TiO3

We synthesized A-site Mn-doped Bi0·5Na0·5TiO3 polycrystalline ceramic ((Bi0·5Na0.5)0.9Mn0·1TiO3 ceramic (BNMT10)) via solid-state reaction route and investigated the structural and temperature-dependent dielectric properties. The dielectric properties of the synthesized samples are explained using the brick-layer model. The relaxation time and corresponding activation energies were obtained through the Arrhenius mechanism by using the imaginary impedance and modulus results. Analysis of the activation energy and other dielectric results suggests that the electric conduction in our BNMT10 sample is due to single and doubly charged oxygen ion vacancy-defects at low and high temperatures, respectively. The grains and grain boundaries contribute to the inherent defect-based conduction mechanism and the dielectric behavior. The electric modulus spectroscopy results discerned the non-Debye type relaxation processes that these processes consist of the localized and long-range relaxation processes. Our results demonstrate that the dielectric behavior of Bi0·5Na0·5TiO3 ceramics can be enhanced through Mn-doping at the A-site.

Lattice Boltzmann simulation of transient blood flow in arterial geometries using a regularised, viscoplastic and shear‐thinning fluid

This paper presents a lattice Boltzmann framework for the transient simulation of blood flow using biologically inspired geometries and pressure boundary conditions. The Kuang-Luo rheological model is used to represent blood as a homogeneous continuum. This model includes the two primary non-Newtonian characteristics of blood, namely viscoplasticity and pseudoplasticity. This paper makes two contributions. First, the numerical challenges associated with zero strain rates and infinite viscosity, as a consequence of the yield stress in the Kuang-Luo model, were addressed by regularising the constitutive equation so that the viscosity tends towards a finite value at low strain rates. A two-relaxation-time operator, which exhibits improved performance over the single-relaxation-time operator and lower computational overhead than the multiple-relaxation-time operator, is employed in the collision process. The recursive relationship between the local strain rate and relaxation rate was addressed by use of an implicit solver for these two quantities. The implemented model was benchmarked against analytic solutions for Poiseuille flow between parallel plates in two dimensions and in a cylindrical tube in three dimensions. More importantly, the transient performance of the implemented model was demonstrated by matching the predicted start-up flow of the Poiseuille flow of a Bingham fluid with the corresponding analytical solution. Second, the numerical developments were applied in the simulation of transient blood flow in complex configurations. The development and implementation of physically inspired pressure profiles highlighted the shortcomings of using a sinusoidal pressure profile in the prediction of velocity and stress distributions. Finally, the simulation of blood flow in a section of a carotid artery indicated a number of flow characteristics that will be of interest to future investigations of clinical problems.

Mechanism of Na-Ion Conduction in the Highly Efficient Layered Battery Material Na2Mn3O7

The ionic conduction properties of the technologically important two-dimensional (2D) layered battery material Na2Mn3O7, with exceptional small-voltage hysteresis between charge and discharge curves, have been investigated as a function of temperature and frequency by an impedance spectroscopy. The detailed analyses of the impedance data in the form of dc-conductivity, ac-conductivity, electrical modulus, dielectric constant and complex polarizability reveal a long-range Na-ionic conductivity with negligible contribution from a local dipole relaxation. A significant enhancement (~10^4 times) of the Na-ion conductivity has been found with the increasing temperature from 353 K to 713 K. The temperature dependent conductivity reveals thermally activated conduction process with activation energies of 0.161 and 0.377 eV over the two temperature regions of 383-518 K and 518-713 K, respectively. AC conductivity study reveals a long-range hopping process for the conduction of charge carriers with a sharp increase of the hopping range at 518 K. The scaling study of the ac-conductivity reveals that the frequency-activated conductivity (above 10^4 Hz at 353 K) is mainly controlled by the critical frequency that increases with the increasing temperature. The Na-ion conduction in Na2Mn3O7 occurs predominantly by a correlated barrier hopping process. Besides, a correlation between ionic conduction and crystal structure has been established by x-ray and neutron diffraction study. We have further shown that the conductivity of Na2Mn3O7 can be enhanced by reduction of the stacking faults in the crystal structure. Our study facilitates the understanding of the microscopic ionic conduction mechanism in the highly efficient 2D battery material Na2Mn3O7 having high energy storage capacity and high structural stability, paving way for the discovery of materials for battery applications.

Slow stretched-exponential and fast compressed-exponential relaxation from local event dynamics

We propose an atomistic model for correlated particle dynamics in liquids and glasses predicting both slow stretched-exponential relaxation (SER) and fast compressed-exponential relaxation (CER). The model is based on the key concept of elastically interacting local relaxation events. SER is related to slowing down of dynamics of local relaxation events as a result of this interaction, whereas CER is related to the avalanche-like dynamics in the low-temperature glass state. The model predicts temperature dependence of SER and CER seen experimentally and recovers the simple, Debye, exponential decay at high temperature. Finally, we reproduce SER to CER crossover across the glass transition recently observed in metallic glasses.

Localized Deep and Shallow Traps of α-Peaks from Thermally Stimulated Current (TSC) Measurement on Thermoplastic Polymers

In this paper, trap levels around the glass transition temperature (Tg) of polymers have been characterized using Thermally Stimulated Current (TSC) technique. Deconvolution on α-peaks of the Tg for PE (-104 °C), plasticized PVC (-35 °C), PMMA (90 °C) and PET (96 °C) were carried out based on the first-order kinetic theory for non-Debye relaxation. Using temperature, T from TSC experimental data, we have successfully separated the α-peaks of the thermoplastic polymers. It is found that the complex curve of α-peaks can composed of four (4) to eight (8) sub peaks. Dominant sub peaks were identified at Tmax = -105 °C, -34 °C, 89 °C and 92 °C for PE, pPVC, PMMA and PET, respectively. These peaks show activation energy, Ea of shallow and deep trap centers ranged from 0.3 eV to 4.6 Ev where they represent the depolarization of localized dipoles and space charges relaxations in the polymers.

Proposal of a generic constitutive model for deformation-dependent dielectric constant of dielectric elastomers

Dielectric elastomers (DEs) are electroactive polymers that could be used as soft actuators, stretchable generators and sensors. Their performance is dependent on both their mechanical and dielectric properties. Particularly, the dielectric constant has been shown to be dependent on the state of mechanical stretch, which has to be comprehensively characterized across different modes of deformation and different classes of DEs. We conduct experiments to characterize the stretch-dependence of dielectric constant for three classes of elastomers: acrylic (VHB), silicone and natural rubber. In our characterization, we selected three distinct modes of mechanical deformation: equal-biaxial, unequal-biaxial and uniaxial. We reviewed the five most common stretch-dependent dielectric constant models and evaluated their fit with our experimental data which were based upon stretch-dependent dielectric constant of elastomers. Comparing all the model fittings, we find that, although the polarization-based lumped parameter model presents the best fit, both localized dipole relaxation and long chain polymer polarization were absent in the model. In view of the statistical long-chain dynamics in elastomers, we therefore propose a generic, semi-empirical inverse power-law relationship to generalize and standardize the characterization of stretch-dependence of dielectric constant along with log–log curve fitting. We hope to establish a consistent and general framework for dielectric characterization of dielectric elastomers.

Dynamics across a Free Surface Reflect Interplay between Density and Cooperative Length: Application to Polystyrene

It is now generally agreed that the most dramatic influence of a free surface on local relaxation dynamics occurs over the first 10 nm from the surface. Using the cooperative free volume (CFV) rate model, we have linked a faster dynamic response to a lower density (i.e., greater available or free volume) closer to the interface. Experimental and simulation studies have shown that the relaxation profile is significantly broader than the local density profile. Here, we explain this difference using the CFV model to show that local relaxation can be enabled through accrual of a fixed amount of free volume, the value of which is a characteristic, material-dependent quantity. The process by which a relaxing segment acquires this volume involves a cooperative region whose length scale will change with density and therefore with distance from the interface. The result is a region-averaged position-dependent density profile that is significantly broadened and that links directly to the relaxation profile. Finally, we explain why these film confinement effects diminish in importance as the temperature is increased.

Low-frequency carrier kinetics in triple cation perovskite solar cells probed by impedance and modulus spectroscopy

Organometallic halide perovskites-based solar cells have emerged as next-generation photovoltaic technology. However, many of its intriguing optoelectronic properties at low frequency are highly debated. Here, we investigate the low-frequency carrier kinetics of the state-of-the-art triple cation perovskite Cs0.06FA0.79MA0.15Pb(I0.85Br0.15)3 solar cells using bias-dependent impedance and modulus spectroscopy under dark and illumination conditions. We observe a strong dependence of dielectric permittivity on frequency in 1 Hz to 1 MHz region with a dielectric relaxation, which is observed to follow the Maxwell-Wagner type interfacial polarization possibly originating from the grain boundary/ionic defects. Furthermore, correlating the impedance and modulus spectra reveals the localized charge carrier relaxation in this triple cation device from which we obtain a phenomenological picture of the hopping process and developing an understanding of the charge carrier kinetics in these high-efficiency perovskite photovoltaics.

A Simple New Way To Account for Free Volume in Glassy Dynamics: Model-Free Estimation of the Close-Packed Volume from PVT Data.

In this article we focus on the important role of well-defined free volume (Vfree) in dictating the structural relaxation times, τ, of glass-forming liquids and polymer melts. Our definition of Vfree = V - Vhc, where V is the total system volume, means the use of Vfree depends on determination of Vhc, the system's volume in the limiting closely packed state. Rejecting the historically compromised use of Vfree as a dynamics-dependent fitting function, we have successfully applied a clear thermodynamics-based route to Vhc using the locally correlated lattice (LCL) model equation of state (EOS). However, in this work we go further and show that Vhc can be defined without the use of an equation of state by direct linear extrapolation of a V(T) high-pressure isobar down to zero temperature (T). The results from this route, tested on a dozen experimental systems, yield ln τ vs 1/Vfree isotherms that are linear with T-dependent slopes, consistent with the general ln τ ∼ f(T) × (1/Vfree) form of behavior we have previously described. This functional form also results by implementing a simple mechanistic explanation via the cooperative free volume (CFV) rate model, which assumes that dynamic relaxation is both thermally activated and that it requires molecular segmental cooperativity. With the degree of the latter, and thus the activation energy, being determined by the availability of free volume, the new route we demonstrate here for determination of Vfree expands the potential for understanding and predicting local dynamic relaxation in glass-forming materials.

Hierarchy recurrences in local relaxation

Inside a closed many-body system undergoing the unitary evolution, a small partition of the whole system exhibits a local relaxation. If the total degrees of freedom of the whole system is a large but finite number, such a local relaxation would come across a recurrence after a certain time, namely, the dynamics of the local system suddenly appear random after a well-ordered oscillatory decay process. It is found in this paper, for a collection of $N$ two-level systems (TLSs), the local relaxation of one TLS within has a hierarchy structure hiding in the randomness after such a recurrence: similar recurrences appear in a periodical way, and the later recurrence brings in stronger randomness than the previous one. Both analytical and numerical results that we obtained well explains such hierarchy recurrences: the population of the local TLS (as an open system) diffuses out and regathers back periodically due the finite-size effect of the bath [the remaining $(N-1)$ TLSs]. We also find that the total correlation entropy, which sums up the entropy of all the $N$ TLSs, approximately exhibit a monotonic increase; in contrast, the entropy of each single TLS increases and decreases from time to time, and the entropy of the whole $N$-body system keeps constant during the unitary evolution.

Early Strides in NMR Dynamics Measurements.

The study of protein dynamics using the measurement of relaxation times by NMR was based on a set of studies in the mid-20th century that outlined theories and methods. However, the complexity of protein NMR was such that these simple experiments were not practical for application to proteins. The advent of techniques in the 1980s for isotopic labeling of proteins meant that pulse sequences could now be applied in multidimensional NMR experiments to enable per-residue information about the local relaxation times. One of the earliest advances was published in Biochemistry in 1989. The paper "Backbone dynamics of proteins as studied by 15N inverse detected heteronuclear NMR spectroscopy: application to staphylococcal nuclease" by Lewis Kay, Dennis Torchia, and Ad Bax delineated a set of pulse sequences that are used with minor modifications even today. This paper, with others from a limited number of other laboratories, forms the basis for the experimental determination of the backbone dynamics of proteins. The biological insights obtained from such measurements have only increased in the past 30 years. Sometimes, the best and perhaps only way to advance a field is an advancement in the technical capabilities that allows new perspectives to be reached.

Intramolecular relaxation of ring polymers in dilute solutions

The intramolecular relaxation dynamics of unconcatenated ring polymers in dilute solutions is theoretically investigated within the framework of the Rouse–Zimm theory. The excluded volume interactions (EVIs) between the nonbonded monomers are modeled by a harmonic potential, where the interaction parameter is evaluated from Flory’s mean-field approach. The hydrodynamic interactions (HIs) between the pairs of monomers are approximated by a preaveraged Oseen tensor. The mechanical moduli are dominated by the smaller relaxation rates corresponding to the collective relaxation modes in the low frequency regime, while they are governed by the higher relaxation rates corresponding to the local relaxation modes in the high frequency regime. EVI decreases the relaxation rates of the normal modes where the decrease for the collective modes is larger than that for the local modes, which consequently expands the width of the relaxation spectrum. The characteristic overall relaxation time is evaluated from the inverse of the crossover frequency, which is the same for rings of various sizes with HI and with both HI and EVI, while it shifts to lower frequencies with increasing ring size for the Rouse rings.