Dependence Of Relaxation Time Research Articles

Solvation Structure and Dynamics of the Thiocyanate Anion in mixed N,N-Dimethylformamide-Water Solvents: A Molecular Dynamics Approach.

The solvation structure and dynamics of the thiocyanate anion at infinite dilution in mixed N, N-Dimethylformamide (DMF)-water liquid solvents was studied using classical molecular dynamics simulation techniques. The results obtained have indicated a preferential solvation of the thiocyanate anions by the water molecules, due to strong hydrogen bonding interactions between the anion and water molecules. A first hydration shell at short intermolecular distances is formed around the SCN- anion consisting mainly by water molecules, followed by a second shell consisting by both DMF and water molecules. The strong interactions between the thiocyanate anion and water molecules are further reflected upon the calculated intermittent residence lifetimes of water and DMF in the first and second solvation shells. The dependence of the reorientational relaxation times of the thiocyanate anion upon the mole fraction of DMF in the mixtures has been found to be in good agreement with experiment, revealing strong concentration effects upon these relaxation phenomena. An appreciable solvent composition effect upon the low frequency intermolecular vibrations, due to the anion-water interactions, has also been revealed by calculating the atomic velocity correlation functions and corresponding spectral densities of the anion.

Operando XRD Observation of NMC Cathode for Reaction Distribution Analysis Under Fast Discharging

Introduction There is a demand for high output power of lithium-ion batteries (LIBs) as regenerative power sources for construction machinery. It is important to analyze electrode behavior during high C-rate discharge processes. The main reason why LIBs do not have sufficient capacity at high power output is thought to be that the discharge finishes when the topmost surface of the electrode reaches the cut-off potential, even if the other parts are only partially discharged.In this study, an attempt was made to infer the reaction distribution and fast response of the entire electrode by observing the relaxation process after discharge using laboratory XRD. Operando XRD measurements were performed for a positive electrode of active material LiNi1/3Mn1/3Co1/3O2 (NMC) while discharging at 0.1C, and a correlation was observed between SOC and the peak angle derived from 101 reflection. By contrasting this with known NMC crystal lattice changes during charging and discharging, compositional changes can be captured [1-3]. Based on this, the behavior of NMC electrodes of various electrode designs during the relaxation process after fast discharge was observed, and the results are reported. Experimental Laminated half-cells (30 mm square) were prepared using NMC electrodes with different electrode designs (thickness and porosity) for the positive electrode, Li metal for the negative electrode, and carbonate electrolyte containing 1.0 mol dm− 3 LiPF6 as the electrolyte solution. The electrodes were made with three electrode thickness levels of approximately 20 µm, 30 µm, and 40 µm (constant porosity), and three porosity levels of approximately 30%, 40%, and 50% (constant loading). After charging these cells to 100% SOC at 0.1C, they were installed in an X-ray diffraction system (SmartLab, Rigaku) and subjected to fast discharge with the charge/discharge device. Discharge conditions were as follows: DOD 50% capacity was discharged at 5C current, followed by 1.5 hours of Relaxation. At the same time, operando XRD measurements were performed to obtain the displacement of the peak top angle originating from the (101) plane of NMC. Result and Discussion The obtained (101) plane peak-top angles and cell voltage displacements are shown in Figure 1. In this case, X-rays were incident from the negative electrode side. It was observed that the peak angle became smaller as the cell discharged and gradually increased during the relaxation. This suggests that the reaction was preceded on the separator-side portion of cathode, leading to the end of discharge, and that the Li imbalance in the electrode was relaxed in the subsequent open circuit state.The same measurements were performed at different levels of NMC electrode thickness and porosity, and the peak angle displacement and relaxation time during the relaxation process were compared. The results showed that there was no clear dependence of peak angle displacement and relaxation time on thickness. On the other hand, the larger the porosity, the smaller the peak angle displacement and the larger the relaxation time. These results indicate that there is a clear correspondence between the electrode design and the reaction inhomogeneity in the electrode, and that this method can be used to evaluate the reaction distribution.In addition, the relationship between the angular displacement of the above XRD peak and the change in cell voltage behavior during the relaxation process was also discussed by fitting with an equivalent circuit. The correlation between the two results suggests the possibility of observing the reaction distribution inside the battery from the analysis of the cell voltage behavior.

Emergent Research Trends on the Structural Relaxation Dynamics of Molecular Clusters: From Structure-Property Relationship to New Function Prediction.

ConspectusMolecular clusters (MCs) are monodispersed, precisely defined ensembles of atom collections featured with shape-persistent architectures that can deliver certain functions independently. Their molecular compositions and surface functionalities can be tailored feasibly in a predefined manner, and they can be applied as basic structural units to be engineered into materials with desirable hierarchical structures and enriched functions. The chemical systems also offer great opportunities for the design and fabrication of soft structural materials without the chain topologies of polymers. The bulks of MC assemblies demonstrate viscoelasticity that is used to be considered as the unique feature of polymers, while the MC systems are distinct from polymers since their elasticities are resilient even at temperatures 100 K above their glass transition temperatures. The understanding of their anomalous viscoelasticity and the extended studies of general structure-property relationships are desired for the development of new chemical systems for emergent functions and the possibilities to resolve the intrinsic trade-offs of traditional materials.Meanwhile, general macroscopic functions or properties of materials are related to the transportation of mass, momentum, and/or energy, and they are basically realized or directed by the motions of structural units at different length scales. Structural relaxation dynamics research is critical in quantifying motions ranging from fast bond deformation, bond break/formation, and diffusion of ions and particles to the cooperative motions of structure units. Due to the advancement of measurement technology for relaxation dynamics (e.g., quasi-elastic scattering and broadband dielectric spectroscopy), the structural relaxation dynamics of MC materials have been probed for the first time, and their multiple relaxation modes across several temporal scales were systematically studied to bridge the correlation between molecular structures and macroscopic functions. The fingerprint information from dynamics studies, e.g., the temperature dependence of relaxation time and certain property, e.g., ion conductivity, was proposed to quantify the structure-property relationship, and the microscopic mechanism on the mechanical properties, ion conduction, and gas absorption and separation of MC materials can be fully understood.In this Account, to elucidate the uniqueness of MC materials, especially in comparison with polymers, four topics are mainly summarized: structural features, relaxation dynamics characterization techniques, relaxation dynamics characteristics, and quantified understanding of the structure-property relationship. The capability for new function prediction from relaxation dynamics studies is also introduced, and the typical example in impact resistant materials is provided. The Account aims to prove the significance of relaxation dynamics characterization for material innovation, while it also confirms the potential of MCs for functional material fabrications.

State-of-the-art Review of Springback Behavior of Polymers

The spring-in and spring-back behavior of polymers is intricate and influenced by various process parameters and mechanisms, including interply slip, anisotropic thermal expansion, and crystallization, all of which can lead to residual stresses. Composite materials made of metal and polymer are being investigated by researchers as a promising alternative to monometallic materials due to their superior properties. However, the number of studies related to metal/polymer/metal laminates on the same topics is relatively limited. A comprehensive review study was carried out with a focus on research works that were conducted with the consideration of different process parameters, such as radius of die and punch, friction, and force applied by blank holder, in order to observe their impact on the springback behavior of polymers. Springback on polymer components depends on the accuracy of appropriate materials and the consideration of appropriate experimental strategies. However, due to their viscoelastic properties, polymers demonstrate distinctive springback behavior. Furthermore, when subjected to deformation, polymers experience a combination of elastic and viscous responses, resulting in immediate elastic recovery and time-dependent viscoelastic relaxation. This intricate behavior presents difficulties in precisely forecasting and managing springback. To enhance the control and optimization of springback in polymer-based manufacturing processes, it is essential to improve the understanding of polymer behavior under diverse loading conditions and to refine simulation techniques accordingly. This review focuses on springback prediction models specific to polymers.

Time-dependent relaxation dynamics of remanent strain in textured PMN–PZ–PT and PMN–PIN–PT piezoceramics

Crystallographically textured lead-based piezoceramics, particularly Pb(Mg1/3Nb2/3)O3–PbZrO3–PbTiO3 (PMN–PZ–PT) and Pb(Mg1/3Nb2/3)O3–Pb(In1/2Nb1/2)O3–PbTiO3 (PMN–PIN–PT), play a pivotal role in electromechanical applications due to their enhanced field-induced strain responses. However, challenges in precision positioning arise from heightened remanent strain (Sr) caused by embedded templates in the textured grains, impacting strain cycle consistency due to increased time delay for Sr relaxation. This study investigates the time-dependent relaxation dynamics of Sr in textured PMN–PZ–PT and PMN–PIN–PT piezoceramics, focusing on experimentally determining relaxation time between cycles required for complete Sr relaxation. Our findings reveal that the relaxation time in textured piezoceramics is notably longer than that in their non-textured counterparts, primarily due to pinning of domain walls by embedded templates. This work provides insights into the strain relaxation characteristics of piezoceramics and underscores the importance of time delay in designing precision positioning systems for improved reliability.

Unveiling the Unusual Electron–Phonon Interaction and Quasi‐Particle Dynamics in type‐II Weyl Semimetal NbIrTe4

AbstractLayered ternary type‐II Weyl semimetals demonstrate promising applications in high‐performance and broadband optoelectronics, therefore it is crucial to gain insights into their photocarriers’ dynamics. In this work, the probing polarization dependence of non‐equilibrium dynamics in NbIrTe4 is investigated by using transient reflectivity spectroscopy. Following photoexcitation at 3.18 eV, the dynamical response of 1.59 eV probe pulse exhibits a strong dependence on probe polarization. The relaxation comprises two components: a rapid recovery of ≈0.6 ps attributed to the electron–phonon scattering, and an anomalous slow recovery spanning hundreds of picoseconds attributed to the photoinduced quasi‐particle. The polarization dependence of rapid relaxation time τ is indicative of the in‐plane anisotropy of electron–phonon coupling in NbIrTe4. The slow relaxation modulated by a latest reported 16 cm−1 coherent phonon also shows strong probing polarization dependence, further revealing the anisotropic nature of electron–phonon coupling and the possibility of anisotropic lattice distortion, as well as photoinduced polaron, under ultrafast photoexcitation in NbIrTe4. The dynamical anisotropy in NbIrTe4 has provided valuable guidance for the application of NbIrTe4 in polarization‐sensitive nonlinear optics or optoelectronic devices and offers insights into the unique carrier transport as well as phonon transport properties of this newly established topological material.

Study of molecular interaction between benzaldehyde and methanol using microwave dielectric relaxation spectroscopy and radial distribution function

A microwave dielectric relaxation study was conducted for mixtures of benzaldehyde (BZ) and methanol (MeOH) over a frequency range of 200 MHz to 20 GHz at seven different temperatures, ranging from 293.15 K to 323.15 K. The dielectric relaxation parameters, obtained through a fitting process, were used to examine their dependence on concentration and temperature. Thermodynamic parameters, such as Gibbs free energy (ΔG), molar enthalpy of activation (ΔH), and molar entropy of activation (ΔS), were evaluated using the temperature dependence of the dipolar relaxation time. The study provided valuable insights into the molecular interactions and dynamic behavior of the components in the binary mixture system. Additionally, a molecular dynamics (MD) simulation study was conducted on the binary mixture of BZ and MeOH to determine the Radial Distribution Function (RDF) and coordination number for different pairs of molecules and atoms, which revealed information about the binding and arrangement of the local structure.

Comparison of two nonlinear formulations of the Maxwell-Cattaneo equation in heat pulse transmission

The nonlinear terms resulting from temperature dependence of thermal conductivity and relaxation time must be considered when studying systems undergoing very short thermal pulses with non-negligible amplitude of the temperature perturbation. Two nonlinear formulations of the Maxwell-Cattaneo-Vernotte equation for thermal transport with relaxation effects are introduced. A comparison of the consequences of these two different nonlinear Cattaneo type equations on thermal pulse propagation is obtained and discussed. The differences in the corresponding velocities and in the corresponding heights of the perturbation peaks turn out to be significant and could be experimentally detected.

On the time-dependent sliding contact behavior of three-phase polymer matrix smart composites

Abstract Three-phase smart composites consisting of magnetostrictive and piezoelectric reinforcements embedded with a polymer matrix can achieve specific multifunctional properties in response to external stimuli, which are well-suited for the application of sensors, actuators, and electronic devices. The materials exhibit complex behaviors characterized by electro-magneto-viscoelasticity coupling during the contact of these smart structures. This paper proposes a novel hybrid element method (HEM) for numerically analyzing the frictionless sliding contact problem stemming from the viscoelastic behavior and multiphase interactions of polymer matrix smart composites. The study aims to fully investigate the effects of material properties, sliding velocities, and action time on the contact behavior of materials via the integration of the conjugate gradient method (CGM) with the discrete convolution-fast Fourier transform (DC-FFT) algorithm. The analytical viscoelastic frequency response functions (FRFs) are derived by substituting elastic solutions with the time-dependent relaxation modulus. Numerical results show that three-phase polymer matrix smart composites exhibit lower contact pressure and higher surface electric/magnetic potential than three-phase magneto-electro-elastic composites. Sliding velocity and action time strongly influence the distribution of pressure/stress and electric/magnetic potential.

NH2(CH3)2CuCl3 Organic-Inorganic Hybrid Perovskite: Consideration to Crystal Structure, Thermodynamics, and Structural Molecular Dynamics.

The crystal structure of NH2(CH3)2CuCl3, an organic-inorganic hybrid perovskite, undergoes a phase transition from triclinic to monoclinic at the phase transition temperature T C of 287 K. We investigated the temperature dependencies of NMR chemical shifts and spin-lattice relaxation time T 1ρ to gain insights into the structural geometry and molecular dynamics during the transition from phase II to phase I at high temperatures. Analysis of the 1H and 13C NMR chemical shifts of the cation revealed a continuous change in the surrounding structural geometry with temperature, without any anomalous changes around T C. The sudden decrease in T 1ρ values from low to high temperatures indicated a significant variation in proton and carbon dynamics at T C, arising from the slowing motion of molecular dynamics across the phase transition. The activation energies E a obtained from the temperature dependence of T 1ρ for 1H and 13C were larger in phase I than in phase II. This suggests that molecular motions in phase II exhibit a higher degree of freedom compared to those in phase I, where they are more constrained. These findings on NH2(CH3)2CuCl3 are presented to enhance its potential applications by elucidating the crystal configuration and structural molecular dynamics of ABX3 type compound.

Non-Debye Behavior of the Néel and Brown Relaxation in Interacting Magnetic Nanoparticle Ensembles.

We used ac-susceptibility measurements to study the superspin relaxation in Fe3O4/Isopar M nanomagnetic fluids of different concentrations. Temperature-resolved data collected at different frequencies, χ″ vs. T|f, reveal magnetic events both below and above the freezing point of the carrier fluid (TF = 197 K): χ″ shows peaks at temperatures Tp1 and Tp2 around 75 K and 225 K, respectively. Below TF, the Néel mechanism is entirely responsible for the superspin relaxation (as the carrier fluid is frozen), and we found that the temperature dependence of the relaxation time, τN(Tp1), is well described by the Dorman-Bessais-Fiorani (DBF) model: τNT=τrexp⁡EB+EadkB T. Above TF, both the internal (Néel) and the Brownian superspin relaxation mechanisms are active. Yet, we found evidence that the effective relaxation times, τeff, corresponding to the Tp2 peaks observed in the denser samples do not follow the typical Debye behavior described by the Rosensweig formula 1τeff=1τN+1τB. First, τeff is 5 × 10-5 s at 225 K, almost three orders of magnitude more that its Néel counterpart, τN~8 × 10-8 s, estimated by extrapolating the above-mentioned DBF analysis. Thus, 1τN≫1τeff, which is clearly not consistent with the Rosensweig formula. Second, the observed temperature dependence of the effective relaxation time, τeff(Tp2), is excellently described by τB-1T=Tγ0exp⁡-E'kBT-T0', a model solely based on the hydrodynamic Brown relaxation, τB(T)=3ηTVHkBT, combined with an activation law for the temperature variation of the viscosity, ηT=η0exp⁡E'/kB(T-T0'. The best fit yields γ0=3ηVHkB = 1.6 × 10-5 s·K, E'/kB = 312 K, and T0' = 178 K. Finally, the higher temperature Tp2 peaks vanish in the more diluted samples (δ ≤ 0.02). This indicates that the formation of larger hydrodynamic particles via aggregation, which is responsible for the observed Brownian relaxation in dense samples, is inhibited by dilution. Our findings, corroborating previous results from Monte Carlo calculations, are important because they might lead to new strategies to synthesize functional magnetic ferrofluids for biomedical applications.

Threshold temperature of superfluorescence generation in CuCl quantum dots under resonant excitation of excitons and resonant two-photon excitation of biexcitons

We studied the threshold temperature of superfluorescence (SF) generation with regard to biexcitons in CuCl quantum dots (QDs) under resonant two-photon excitation of biexcitons and resonant excitation of excitons to demonstrate the influence of initial population densities in the QDs on SF generation. As a result, the threshold temperature under the resonant excitation of excitons was higher than that under the two-photon excitation of biexcitons. This indicates that the high density of excited dots facilitates the rapid establishment of coherence among the dots, overcoming disadvantages of incomplete population inversion and formation process of biexcitons. We performed a theoretical calculation of the time profiles of the biexcitonic emission based on semiconductor luminescence equations. The experimentally obtained temperature dependence of the time profiles was qualitatively reproduced by calculating their dependence on the dephasing rate. In addition, we estimated the temperature dependence of the phase relaxation time of the biexcitons in the CuCl QDs by analyzing the temperature dependence of SF.

Impact of Nickel doping on microstructure and impedance spectroscopy of multiferroic YCrO3

In this work, we study the effect of Ni-doping on the structural and impedance spectroscopy properties of the polycrystalline YCrO3 ceramic sample. The structural analysis shows all the samples crystallize in an orthorhombic structure with the Pnma space group. The depressed and asymmetric semicircle of complex impedance spectra indicates that the relaxation of charge carriers is of non-Debye type, where the thermally activated charge carriers control it. The temperature dependence of relaxation time and electrical conductivity exhibit an anomaly in the vicinity of diffuse-like relaxor transition temperature (TC ∼ 460 K). The analysis of conductivity data shows hopping-type charge conduction. The analysis further indicates that while the dc conductivity increases continuously, the activation energy shows a non-monotonous variation with Ni concentration.

Thermo-mechanical response of near-pearlitic steel heated under restriction of thermal expansion

Railway wheels experience high temperatures during operation, especially during severe block braking. The thermal expansion of wheel rim material due to frictional heating is limited by the wheel's geometry and size. This study investigated the impact of this combined mechanical and thermal loading on the mechanical properties and microstructure in the tread surface of an ER7T steel railway wheel.The material response below the austenitisation temperature is comprehensively evaluated through thermal cycling at peak temperatures of 300, 400, 600, and 650 °C, simulating severe block braking cycles with varying degrees of thermal dilatation (25 %, 50 %, 75 %, and 100 %). An initial plastic deformation was observed during the first heating cycle for the two lower temperatures at lower restrictions, followed by a predominantly elastic response. However, at higher restrictions, the material showed time-dependent relaxation during heating, and some plastic deformation was observed during cooling. Notably, even at the lowest level of restriction, similar observations were made at higher peak temperatures. Increasing the restriction resulted in large strains and a wider hysteresis loop. The test bars exposed to the two higher temperatures retained large tensile stresses after cooling. This indicates a risk of a significantly altered residual stress state in the rim of an overheated railway wheel, which could adversely affect its fatigue properties. The study's outcomes will aid in designing and calibrating constitutive material models for severe block braking. Furthermore, it will significantly contribute to research into the thermo-mechanical behaviour of pearlitic/near-pearlitic materials during railway operations and maintenance.

Microscopic Observation of the Anisotropy of the Johari-Goldstein-β Process in Cross-Linked Polybutadiene on Stretching by Time-Domain Interferometry.

The strain dependence of the Johari-Goldstein (JG)-β relaxation time, as well as the directional dependence, was systematically investigated for stretched cross-linked polybutadiene using time-domain interferometry. We found that the strain dependence of the JG-β relaxation time is directionally dependent, contrary to expectation: the relaxation time of the JG-β motion, whose displacement is perpendicular to the stretching direction, decreases with stretching, whereas the relaxation time of the parallel JG-β motion changes little. This result is distinct from the previously reported strain dependence of the α relaxation time, where the relaxation time increases isotropically with stretching. Thus, the difference in the strain dependence of the relaxation time between the α and JG-β processes suggests a microscopic origin and requires the modification of the conventional dynamic picture for stretched polymers.

Investigation of the temperature dependence of the dielectric relaxation of chlorobenzene, bromobenzene and iodobenzene

This paper deals with the investigation results of temperature dependence of complex permittivity’sε∗ = έ − iε˝ of chloro, bromo and iodo- benzene at wavelength 11,50 cm and 12,80 cm within the temperature range 20 ÷ -80˚. It is established that dielectric properties of given liquids are characteristic of one relaxation time. The dielectric spectra were studied taking into account other frequencies given in the literature. In all investigated liquids, a jump appears in the real and imaginary parts of the complex permittivity at the point of the phase transition. The temperature dependence of the dielectric relaxation time of molecules in the liquid state has been determined. It was found that with an increase in the amount of the halogen substituent, an increase in the relaxation time occurs. Macroscopic and molecular relaxation times were calculated from the experimental values. The thermodynamic quantities characterizing the process of dielectric relaxation are calculated. The activation enthalpy of dielectric relaxation processes is compared. The studies were carried out using the dielectric spectroscopy method. This method allows a more detailed study of the dielectric properties of the objects of study due to the large equilibrium (“static”) dielectric constant of the object. It has been determined that the height of the potential barrier separating the two equilibrium positions of a polar molecule is greatest in the state of a pure polar liquid and decreases with dilution in a non-polar solvent.

Ultrafast carrier dynamics and nonlinear optical absorption of two-dimensional NiPS3 nanosheets

Two-dimensional (2D) materials have been extensively explored for various optoelectronic devices, showing tremendous application potential. Metal phosphorus trichalcogenide compounds are new intrinsic magnetic semiconductor materials that possess unique and excellent physical and optical properties. Among them, NiPS3 has a bandgap of 1.6 eV and is an intrinsic antiferromagnetic semiconductor. In our work, the nonlinear optical absorption and carrier dynamics of 2D NiPS3 nanosheets are studied by the I-scan system and time-resolved transient transmission spectroscopy. The thickness-dependent carrier relaxation time is obtained utilizing the pump-probe technique. The strong dependence of slow relaxation time on incident intensity is also reflected in the thick sample, which distinguishes the lattice thermal diffusion in 2D nanosheets from that of bulk. The saturation absorption and two-photon absorption coefficients are further achieved. Our results provide a perspective for the applications of NiPS3 nanosheets in optical devices such as micro saturable absorbers and on-chip ultrafast optical switches.

Tuning the Superspin Dynamics in Inverse Spinel Ferrite Nanoparticle Ensembles via Indirect Cation Substitution

We used magnetic and synchrotron X-ray diffraction measurements to investigate the possibility of tuning the strength of magnetic interparticle interactions in nanoparticle ensembles via chemical manipulation. Our main result comes from temperature-resolved in-phase ac-susceptibility data collected on 8 nm average-diameter Ni0.25Zn0.75Fe2O4 (Ni25) and Ni0.5Zn0.5Fe2O4 (Ni50) nanoparticles at different frequencies, χ′ vs. T|f. We found that the relative peak temperature variation per frequency decade, ϕ=∆TT·∆log(f)—a known measure of interparticle interaction strength—exhibits a four-fold increase, from ϕ = 0.04 in Ni50 to ϕ = 0.16 in Ni25. This corresponds to a fundamental change in the nanoparticles’ superspin dynamics, as proven by the fit of phenomenological models to magnetic relaxation data. Indeed, the Ni25 ensemble exhibits superparamagnetic behavior, where the temperature dependence of the superspin relaxation time, τ, is described in the Dorman–Bessais–Fiorani (DBF) model: τT=τrexp⁡EB+EadkBT, with parameters τr = 4 × 10−12 s, and (EB + Ead)/kB = 1473 K. On the other hand, the nanoparticles in the Ni50 ensemble freeze collectively upon cooling in a spin-glass fashion according to a critical dynamics law: τ(T)=τ0TTg−1zν, with τ0 = 4 × 10−8 s, Tg = 145 K, and zν = 7.2. Rietveld refinements against powder X-ray diffraction data reveal the structural details that underlie the observed magnetic behavior: an indirect cation replacement mechanism by which non-magnetic Zn ions are incorporated in the tetrahedral sites of the inverse spinel.

Electronic and magnetic properties of Zn1−xMnxSe:Fe2+,Cr2+ (x = 0.3) single crystals

We report the first study of Zn1−xMnxSe:Fe2+,Cr2+ (x = 0.3) crystals by continuous wave (CW) and pulsed electron paramagnetic resonance (EPR) spectroscopic techniques. Using the advantages of pulsed EPR, spin Hamiltonian parameters for Mn2+ ions were obtained (g∥ = g⊥ = 2.0060(3), А∥ = А⊥ = 61.84·10–4 cm–1, and D = –7.1·10–4 cm–1). The temperature dependence of the spin relaxation times of Mn2+ ions was described using the Orbach process for TM–1 and the Raman mechanisms for T1–1. The spin Hamiltonian parameters for Cr2+ ions were determined from the analysis of the angular dependence of CW EPR spectra (g⊥ = 1.98, g∥ = 1.961, D = –2.48 cm–1, and a = 0.02 cm–1). Moreover, an anisotropic ferromagnetic resonance (FMR) line was observed, the nature of which has yet to be clarified.

Ferroelectric and antiferroelectric chiral multilactate liquid crystalline materials with negative dielectric anisotropy

In this work, the mesomorphic, electro-optic and dielectric properties have been discussed in the light of molecular structure-property correlations of two chiral multilactate liquid crystalline materials possessing the orthogonal paraelectric Smectic A* phase, tilted ferroelectric Smectic C* phase and the tilted antiferroelectric Smectic CA* phase, over a substantially broad temperature range. Interestingly, a reasonably rare re-entrant Smectic C* phase (SmCre*) has also been identified in one of the investigated materials. These materials differ in their linkage groups (keto or ether) and an additional chiral unit in the terminal chain. The phase transition temperatures and transition enthalpies were determined from Polarizing Optical Microscopy and Differential Scanning Calorimetry (DSC) measurements. The compounds exhibit negative dielectric anisotropy (Δε) throughout the mesomorphic range (maximum −18 and −4 in SmA* for both the compounds) and moderately high values of spontaneous polarization (∼153 nC/cm2 in SmCre* phase). The temperature dependence of the response time (τ), bulk viscosity (η) and the activation energies (Ea) throughout the mesomorphic phase have been determined from the spontaneous polarization measurements. To emphasize the structure-property correlations in more detail, dielectric spectroscopy measurement has also been performed to measure the dielectric strength, dielectric loss, frequency dependent permittivities, relaxation time and relaxation frequencies. The clear evidence of the relatively rare SmCre* phase has also been confirmed from the temperature and frequency dependence of the dielectric permittivity. These results shed important light on the emergence of these materials as a smart alternative for their application in multicomponent mixtures targeted for advanced electro-optic and photonic devices.