Frequency-dependent Relaxation Research Articles

Frequency-Dependent Vibrational Relaxation Time of OH Stretch at the Air/Isotopically Diluted Water Interface.

Elucidation of the vibrational relaxation process of interfacial water is indispensable for understanding energy dissipation at the aqueous interface. In this study, the vibrational relaxation dynamics of the hydrogen-bonded OH (HB OH) stretch vibration was investigated at the air/isotopically diluted water (HOD-D2O) interface by time-resolved heterodyne-detected vibrational sum frequency generation (TR-HD-VSFG) spectroscopy. We observed the temporal change of the excited-state band (v = 1 → 2 transition), which enables a reliable determination of the T1 time of interfacial water. The T1 times obtained for the HB OH stretch with various pump frequencies are 0.14 ± 0.15 ps (3200 cm-1), 0.27 ± 0.05 ps (3300 cm-1), 0.34 ± 0.03 ps (3400 cm-1), and 0.63 ± 0.04 ps (3500 cm-1), indicating that T1 is comparable with the value at the air/H2O interface at the low-frequency side but is markedly longer at the high-frequency side. The observed frequency-dependent T1 time can be rationalized in terms of the frequency mismatch between the HB OH stretch and the bending overtone in HOD-D2O, supporting the conclusion that vibrational relaxation through the Fermi resonance with the bending overtone is the predominant mechanism of the vibrational relaxation of the HB OH stretch at the air/water interface.

Translational Dynamics of Cations and Anions in Ionic Liquids from NMR Field Cycling Relaxometry: Highlighting the Importance of Heteronuclear Contributions.

NMR field cycling relaxometry is a powerful method for determining the rotational and translational dynamics of ions, molecules, and dissolved particles. This is in particular true for ionic liquids (ILs) in which both ions carry NMR sensitive nuclei. In the IL triethylammonium bis(trifluoromethanesulfonyl)imide ([TEA][NTf2]), there are 1H nuclei at the [TEA]+ cations and 19F nuclei at the [NTf2]- anions. Moreover, the high viscosity of this IL leads to frequency-dependent relaxation rates, leaving the so-called extreme narrowing regime. Both the rotational and the translational dynamics of the constituents of ILs can be obtained by separating the contributions of intra- and intermolecular relaxation rates. In particular, the translational dynamics can be obtained separately by applying the so-called "low-frequency approach" (LFA), utilizing the fact that the change in the total relaxation rates at low frequencies results solely from translational motions. However, for systems containing multiple NMR active nuclei, heteronuclear interactions can also affect their relaxation rates. For [TEA][NTf2], the intermolecular relaxation rate is either the sum of 1H-1H cation-cation and 1H-19F cation-anion interactions or the sum of 19F-19F anion-anion and 19F-1H anion-cation interactions. Due to the lack of available experimental information, the 1H-19F heteronuclear intermolecular contribution has often been neglected in the past, assuming it to be negligible. Employing a suitable set of ILs and by making use of isotopic H/D substitution, we show that the 1H-19F heteronuclear intermolecular contribution in fact cannot be neglected and that the LFA cannot be applied to the total 1H and total 19F relaxation rates.

Impact of CeO2 additive on the temperature and frequency-dependent relaxation and conduction mechanism of BNT-BT ceramic

Impact of CeO2 additive on the temperature and frequency-dependent relaxation and conduction mechanism of BNT-BT ceramic

Electrical transport and dielectric relaxation mechanism in Zn0.5Cd0.5Fe2O4 spinel ferrite: A temperature- and frequency-dependent complex impedance study

In the present study, the frequency-dependent dielectric relaxation and electrical conduction mechanisms in sol-gel-derived Zn0.5Cd0.5Fe2O4 (ZCFO) spinel ferrite were studied in the temperature range of 343–438 K. The formation of the ZCFO spinel ferrite phase with space group Fd3m was confirmed by X-ray diffraction analysis. The dielectric relaxation and electrical conduction mechanisms were studied using complex impedance spectroscopy (CIS). In the Nyquist plots, depressed semicircles were fitted with an equivalent circuit model with configuration (RGBQGB) (RGQG), signifying the contributions from grain boundaries and grains to the charge transport mechanism in the sample. The frequency-dependent AC conductivity was found to follow Jonscher's power law, and the frequency exponent term depicted the overlapping large polaron hopping (OLPH) model as the dominant transport mechanism. The activation energies for conductivity, electric modulus and impedance were calculated to identify the nature of the charge carriers governing the relaxation and conduction mechanisms in the prepared sample. Complex modulus studies confirmed the non-Debye type of dielectric relaxation, whereas tangent loss and dielectric constant analyses confirmed the thermally activated hopping mechanism of charge carriers in Zn0.5Cd0.5Fe2O4 spinel ferrite.

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.

Structure-property studies of a four coordinate niobium(IV) amide

The preparation, structure, and magnetic properties of Nb[N(Dipp)TMS]2Cl2 (1) are described. The paramagnetic complex is obtained via treatment of NbCl4(THF)2 with two equivalents of Li[N(Dipp)TMS]. Magnetic studies indicate NbIV (S = ½) ions are present and that slow frequency-dependent magnetization relaxation dynamics are operative below ca. 25 K, under application of non-zero magnetic fields. The relaxation dynamics appear to proceed via a Raman pathway.

Exploring low-temperature dynamics in triple perovskite ruthenates using nonlinear dielectric susceptibility measurements

We report the nonlinear dielectric properties of three triple-perovskite ruthenates: Ba3CoRu2O9, Ba3BiRu2O9, and Sr3CaRu2O9. These compounds exhibit notable correlations among their spin, charge, lattice, and polar degrees of freedom. Ba3CoRu2O9 displays a pronounced frequency-dependent relaxation in χ2,3 just above the magnetoelastic transition, occurring around 100 K, followed by an abrupt loss of polarization within the ordered phase. In Ba3BiRu2O9, we encounter the possibility of multiple coexisting relaxation behaviors, indicating a complex phase strongly influenced by the spin-gap opening at 175 K. Lastly, Sr3CaRu2O9 displays anomalies with strong dispersion effects close to its magnetic transitions, indicating a robust coupling between magnetic and dipolar orders in the system. These measurements highlight the significance of higher-order (hyper-)susceptibilities in providing profound insight into the dynamics of a system, offering information otherwise inaccessible through the linear polarization response alone.

Computing the frequency-dependent NMR relaxation of 1H nuclei in liquid water.

We present a computational framework for reliably determining the frequency-dependent intermolecular and intramolecular nuclear magnetic resonance (NMR) dipole-dipole relaxation rates of spin 1/2 nuclei from Molecular Dynamics (MD) simulations. This approach avoids the alterations caused by the well-known finite-size effects of translational diffusion. Moreover, a procedure is derived to control and correct for effects caused by fixed distance-sampling cutoffs and periodic boundary conditions. By construction, this approach is capable of accurately predicting the correct low-frequency scaling behavior of the intermolecular NMR dipole-dipole relaxation rate and thus allows for the reliable calculation of the frequency-dependent relaxation rate over many orders of magnitude. Our approach is based on the utilization of the theory of Hwang and Freed for the intermolecular dipole-dipole correlation function and its corresponding spectral density [L.-P. Hwang and J. H. Freed, J. Chem. Phys. 63, 4017-4025 (1975)] and its combination with data from MD simulations. The deviations from the Hwang and Freed theory caused by periodic boundary conditions and sampling distance cutoffs are quantified by means of random walker Monte Carlo simulations. An expression based on the Hwang and Freed theory is also suggested for correcting those effects. As a proof of principle, our approach is demonstrated by computing the frequency-dependent intermolecular and intramolecular dipolar NMR relaxation rates of 1H nuclei in liquid water at 273 and 298K based on the simulations of the TIP4P/2005 model. Our calculations are suggesting that the intermolecular contribution to the 1H NMR relaxation rate of the TIP4P/2005 model in the extreme narrowing limit has previously been substantially underestimated.

Electric field modulation of ERK dynamics shows dependency on waveform and timing

Different exogenous electric fields (EF) can guide cell migration, disrupt proliferation, and program cell development. Studies have shown that many of these processes were initiated at the cell membrane, but the mechanism has been unclear, especially for conventionally non-excitable cells. In this study, we focus on the electrostatic aspects of EF coupling with the cell membrane by eliminating Faradaic processes using dielectric-coated microelectrodes. Our data unveil a distinctive biphasic response of the ERK signaling pathway of epithelial cells (MCF10A) to alternate current (AC) EF. The ERK signal exhibits both inhibition and activation phases, with the former triggered by a lower threshold of AC EF, featuring a swifter peaking time and briefer refractory periods than the later-occurring activation phase, induced at a higher threshold. Interestingly, the biphasic ERK responses are sensitive to the waveform and timing of EF stimulation pulses, depicting the characteristics of electrostatic and dissipative interactions. Blocker tests and correlated changes of active Ras on the cell membrane with ERK signals indicated that both EGFR and Ras were involved in the rich ERK dynamics induced by EF. We propose that the frequency-dependent dielectric relaxation process could be an important mechanism to couple EF energy to the cell membrane region and modulate membrane protein-initiated signaling pathways, which can be further explored to precisely control cell behavior and fate with high temporal and spatial resolution.

Large Electromechanical Response in a Polycrystalline Alkali-Deficient (K,Na)NbO3 Thin Film on Silicon.

The demand for large electromechanical performance in lead-free polycrystalline piezoelectric thin films is driven by the need for compact, high-performance microelectromechanical systems (MEMS) based devices operating at low voltages. Here we significantly enhance the electromechanical response in a polycrystalline lead-free oxide thin film by utilizing lattice-defect-induced structural inhomogeneities. Unlike prior observations in mismatched epitaxial films with limited low-frequency enhancements, we achieve large electromechanical strain in a polycrystalline (K,Na)NbO3 film integrated on silicon. This is achieved by inducing self-assembled Nb-rich planar faults with a nonstoichiometric composition. The film exhibits an effective piezoelectric coefficient of 565 pm V-1 at 1 kHz, surpassing those of lead-based counterparts. Notably, lattice defect growth is substrate-independent, and the large electromechanical response is extended to even higher frequencies in a polycrystalline film. Improved properties arise from unique lattice defect morphology and frequency-dependent relaxation behavior, offering a new route to remarkable electromechanical response in polycrystalline thin films.

Effect of sintering temperature on impedance and EMI shielding of carbon modified CoFe2O4 nanofibers via electrospinning

The electrospinning technique is employed for the synthesized cobalt ferrite/carbon nanofibers, utilizing iso-propanol as the solvent. The nanofibers prepared are subjected to sintering at three different temperatures. A comprehensive analysis is carried out on the structural, morphological, dielectric, impedance, and electromagnetic shielding effectiveness within the X-band frequency range (8.2–12.4 GHz). The application of the Debye-Scherer formula yielded an estimated crystallite size of 22 nm. The electrical response of cobalt ferrite/carbon nanofibers pellet is characterized by employing impedance spectroscopy. Variations in impedance plane plots are discussed based on frequency dependent relaxation time modulations. The impact of sintering temperature is observed in terms of increased impedance values and modifications in the conduction mechanism. These changes are contributed to distinct hopping carriers’ linkages between Fe3+-Fe2+ and Co3+-Co2+ ions. Dielectric studies are elucidated considering cation polarizability, colossal resistivity, and tangent loss. This study revealed notable characteristics of CoFe2O4/C nanofibers, including colossal resistivity (8.45 × 108 Ωcm), a dielectric constant of 22, and colossal tangent loss. The CoFe2O4/C nanofibers exhibit a characteristic electromagnetic interference (EMI) shielding performance of 30–35 dB. This remarkable shielding performance is observed in nanofibers with a 3 mm thickness, specifically in sample S1 that underwent sintering at a low temperature. The shielding effectiveness is demonstrated within the X-band frequency range.

Small polaron hopping transport mechanism, dielectric relaxation and electrical conduction in NiAl2O4 electro-ceramic spinel oxide

In this study, the frequency and temperature dependent dielectric relaxation and electrical conduction mechanisms in NiAl2O4 spinel oxide ceramic have been explored in a frequency range of over a measured temperature from 163–283 K. The polycrystalline NiAl2O4 was synthesized via solid state reaction route and sintered at 1000 °C. The room temperature x-ray powder diffraction pattern confirmed the formation of NiAl2O4 spinel phase with Fd3m space group. The surface morphology of the sample was investigated by scanning electron microscopy and chemical properties by Fourier transform infrared spectroscopic analysis. Complex impedance studies revealed the presence of relaxation time distribution and charge carriers were found to be thermally activated. The Nyquist plots exhibited depressed semicircles and their fitting by an equivalent circuit model with configuration (RGCG)(RGBCGB) resolved the contributions of grains and grain-boundaries to the electrical transport properties of the material. Electrical conductivity analysis followed the Jonscher’s power law behavior and the frequency exponent suggested small polaron hopping as the governing transport mechanism in NiAl2O4 spinel oxide. Non-Debye type nature of dielectric relaxation was confirmed by the complex modulus analysis whereas dielectric constant and tangent loss analysis verified that the hopping mechanism was thermally activated.

The contribution of lysophosphatidic acid receptors in the response of human lower esophageal sphincter under the electrical field stimulation

BackgroundThis study aims to identify the impact on the reaction while the clasp and sling fibers of the human lower esophageal sphincter are under the electrical field stimulation, by adding lysophosphatidic acid receptor subtypes antagonist.MethodsBetween March 2018 to December 2018, muscle strips were isolated from 28 patients who underwent esophagectomy for mid-third esophageal carcinomas. Muscle tension measurement technique in vitro and electrical field stimulation were used to examine the effects of selective lysophosphatidic acid receptor antagonist on the clasp and sling fibers of human lower esophageal sphincter.ResultsThe optimal frequency of frequency-dependent relaxation in clasp fibers and contraction in sling fibers induced by electrical field stimulation is 64 Hz and 128 Hz respectively. The selective lysophosphatidic acid 1 and 3 receptor antagonist produced no significant difference in the frequency-dependent relaxation in clasp fibers and contraction in sling fibers induced by the electrical field stimulation (P > 0.05).ConclusionThe electrical field stimulation induced a frequency-dependent relaxation in clasp fibers and contraction in sling fibers. The lysophosphatidic acid 1 and 3 receptors are not involved in the response of clasp and sling fibers of the human lower esophageal sphincter induced by the electrical field stimulation.

Ion/Water Network Structural Dynamics in Highly Concentrated Lithium Chloride and Lithium Bromide Solutions Probed with Ultrafast Infrared Spectroscopy

The structural dynamics of highly concentrated LiCl and LiBr aqueous solutions were observed from 1-4 to 1-16 water molecules per ion pair using ultrafast polarization-selective pump-probe (PSPP) experiments on the OD stretch of dilute HOD. At these high salt concentrations, an extended ion/water network exists with complex structural dynamics. Population decays from PSPP experiments highlight two distinct water components. From the frequency-dependent amplitudes of the decays, the spectra of hydroxyls bound to halides and to water oxygens are obtained, which are not observable in the FT-IR spectra. PSPP experiments also measure frequency-dependent water orientational relaxation. At short times, wobbling dynamics within a restricted angular cone occurs. At high concentrations, the cone angles are dependent on frequency (hydrogen bond strength), but at higher water concentrations (>10 waters per ion pair), there is no frequency dependence. The average cone angle increases as the ion concentration decreases. The slow time constant for complete HOD orientational relaxation is independent of concentration but slower in LiCl than in LiBr. Comparison to structural MD simulations of LiCl from the literature indicates that the loss of the cone angle wavelength dependence and the increase in the cone angles as the concentration decreases occur as the prevalence of large ion/water clusters gives way to contact ion pairs.

Dielectric relaxation and dielectric decrement in ionic acetamide deep eutectic solvents: Spectral decomposition and comparison with experiments.

Frequency-dependent dielectric relaxation in three deep eutectic solvents (DESs), (acetamide+LiClO4/NO3/Br), was investigated in the temperature range, 329 ≤ T/K ≤ 358, via molecular dynamics simulations. Subsequently, decomposition of the real and the imaginary components of the simulated dielectric spectra was carried out to separate the rotational (dipole-dipole), translational (ion-ion), and ro-translational (dipole-ion) contributions. The dipolar contribution, as expected, was found to dominate all the frequency-dependent dielectric spectra over the entire frequency regime, while the other two components together made tiny contributions only. The translational (ion-ion) and the cross ro-translational contributions appeared in the THz regime in contrast to the viscosity-dependent dipolar relaxations that dominated the MHz-GHz frequency window. Our simulations predicted, in agreement with experiments, anion-dependent decrement of the static dielectric constant (ɛs ∼ 20 to 30) for acetamide (ɛs ∼ 66) in these ionic DESs. Simulated dipole-correlations (Kirkwood g factor) indicated significant orientational frustrations. The frustrated orientational structure was found to be associated with the anion-dependent damage of the acetamide H-bond network. Single dipole reorientation time distributions suggested slowed down acetamide rotations but did not indicate presence of any "rotationally frozen" molecule. The dielectric decrement is, therefore, largely static in origin. This provides a new insight into the ion dependence of the dielectric behavior of these ionic DESs. A good agreement between the simulated and the experimental timescales was also noticed.

Effect of size of CdO on bias dependent conduction and relaxation mechanism by means of impedance spectroscopy: Experimental and theoretical studies

In this report, the morphological impact of hydrothermally derived CdO on charge conduction and relaxation is investigated by using bias-dependent impedance spectroscopy (IS). The work of art is the findings of the impact of grain and grain boundaries of CdO on the frequency-dependent electric conductivity and relaxation mechanism followed by the crystallite size. In this regard, two different crystallite size based CdOs are derived from hydrothermal route at different temperatures. Materials are characterized by XRD, FESEM, UV–vis absorption spectra. The dc conductivity is also evaluated by measuring current-voltage characteristics, and bias-dependent Impedance Spectroscopy at room temperature, which spectacles the CdO with larger crystallite size dominate the conduction mechanism.

Investigation of optical properties of zinc oxide nanocrystalline materials

The optical properties of Zinc Oxide (ZnO) nanowires are studied using two parallel channels of photon conduction. First is the coherent motion of electrons within the ZnO nanowire termed as Drude carriers and second is the incoherent hopping of electrons from one ZnO nanowire to another nanowire. The model has the relaxation rate as one of the material dependent free physical parameters. The frequency-dependent relaxation rates are presented in terms of memory functions. A peak in optical conductivity obtained near zero-frequency, which occurs due to Drude carriers, i.e., the incoherent motion of electrons whereas, frequency becomes saturated at very-low values at higher frequencies near the far-infrared region. A peak in optical conductivity is observed around mid-infrared frequencies due to the hopping of carriers from one ZnO nanoparticle to another. This is evidenced that both the Drude and hopping carriers contribute to optical conductivity in ZnO nanowire. The modal based on these two contribution schemes successfully explains the optical conductivity phenomena in ZnO nanowires.

Panoramic Mapping of Phonon Transport from Ultrafast Electron Diffraction and Scientific Machine Learning.

One central challenge in understanding phonon thermal transport is a lack of experimental tools to investigate frequency-resolved phonon transport. Although recent advances in computation lead to frequency-resolved information, it is hindered by unknown defects in bulk regions and at interfaces. Here, a framework that can uncover microscopic phonon transport information in heterostructures is presented, integrating state-of-the-art ultrafast electron diffraction (UED) with advanced scientific machine learning (SciML). Taking advantage of the dual temporal and reciprocal-space resolution in UED, and the ability of SciML to solve inverse problems involving coupled Boltzmann transport equations, the frequency-dependent interfacial transmittance and frequency-dependent relaxation times of the heterostructure from the diffraction patterns are reliably recovered. The framework is applied to experimental Au/Si UED data, and a transport pattern beyond the diffuse mismatch model is revealed, which further enables a direct reconstruction of real-space, real-time, frequency-resolved phonon dynamics across the interface. The work provides a new pathway to probe interfacial phonon transport mechanisms with unprecedenteddetails.

Dynamics of a PEG based polymer gel Electrolyte: A combined frequency dependent dielectric relaxation and Time-resolved fluorescence spectroscopic study

• Industrially relevant polymer gel electrolyte studied via dielectric relaxation and time-resolved fluorescence spectroscopy. • Relaxation dynamics monitored by using non-reactive fluorescent probe coumarin153. • Prominent impact of polymer concentration on solution dynamics. • Decoupling of probe solvation dynamics from medium viscosity and probe rotational dynamics. • Signatures of temporal heterogeneity in these polymer gel electrolyte systems observed. Here we investigate the dynamics of a polyethylene glycol ( P E G ) based polymer gel electrolyte (PGE) media and its dependence on polymer concentration and temperature via frequency dependent dielectric relaxation (DR) and time-resolved fluorescence (TRF) spectroscopic measurements. The polymer gel electrolyte system consists of propylene carbonate (PC; organic solvent), lithium perchlorate ( L i C l O 4 ; electrolyte) and P E G 300 (polymer). The impact of polymer on the dynamics of the medium has been monitored via gradually increasing the polymer concentration in the PGE media keeping the P C / L i C l O 4 molar ratio (11.2) unchanged. Coumarin 153 ( C 153 ), a well-known fluorescent probe molecule, has been employed as a local reporter for the fluorescence based experiments. Although the static dielectric constant of the medium decreases systematically upon addition of P E G 300 in the electrolyte media, no such systematic variation with polymer concentration in the fractional power dependence of the measured average DR time with medium viscosity is observed for these electrolyte systems. Steady state fluorescence measurements in these PGE systems indicate substantial effect of polymer addition on the organic electrolyte system, while no signature of spatial heterogeneity has been detected up to 40 wt% polymer concentration. Interestingly, fractional power dependence, similar to DR findings, of average rotational time for C 153 on the medium viscosity has been observed for both the processes, one by varying temperature of the medium at a fixed polymer concentration and other by changing the polymer concentration at a fixed temperature. Surprisingly, the average solvation time shows negative power dependence to the temperature reduced medium viscosity.

Electrical Conductivity Properties of Solid Polymer Electrolytes PEO-PVP-NaIO4 Filled with TiO2 Nanoparticles

Frequency-dependent conductivity and conduction relaxation in nanocomposite solid polymer electrolyte films consisting of poly(ethylene oxide) and polyvinyl pyrrolidone blend as host matrix, NaIO4 as ions dopant, and titanium dioxide (TiO2) nanoparticles of average size 10 nm, were studied. The films were characterized using measurements of complex electrical impedance spectra in the frequency range from 1 Hz to 1 MHz, at room temperature. The concentration of the salt NaIO4 was 10 wt%, the TiO2 percentage varied from 1 wt% to 5 wt%. The frequency spectra of both alternating-current (AC) conductivity and electric modulus were analyzed in order to elucidate the effect of TiO2 nanoparticles on the electrical transport properties of the examined electrolyte thin films with a thickness of 150 μm.