Complex Dielectric Spectra Research Articles

A dielectric, thermodynamic and volumetric investigation for heteromolecular hydrogen bonding in 2-ethoxyethanol and ethanol binary mixture

ABSTRACT The dielectric, thermodynamic and volumetric measurements of neat 2-ethoxyethanol, neat ethanol and their binary mixtures have been carried out using time domain technique at 10°C–25°C with a variation of 5°C. Various dielectric parameters are calculated from complex dielectric spectra and are used to compute Kirkwood correlation factor, Bruggeman factor and activation thermodynamic parameters. These parameters are used to predict heteromolecular hydrogen bonding between associating molecules. The classical and non-classical type H-bonding interactions among the molecules are predicted using FT-IR spectroscopy.

Dielectric analysis of unpolymerized and photopolymerized NOA65 in a parallel-plate cell

The flourishing development of liquid crystal research in recent decades has highlighted the importance of polymer materials in enhancing liquid–crystal material and device properties, demonstrating tremendous potential in a wide range of industries. One of the polymer materials widely used in polymer-dispersed liquid crystal is Norland UV-curable optical adhesive (NOA65). This study focuses on the dielectric behavior of the optical adhesive in a parallel-plate cell. Given the broadness and asymmetry of the dielectric dispersion curve, the two-relaxation Havriliak–Negami model was employed to analyze the complex dielectric spectra of NOA65 before and after photocuring. Experimental results indicate that as temperature rises, the dielectric relaxation of NOA65 undergoes a blue shift, leading to an eventual overlap with pseudo-dielectric relaxation at a higher frequency. This brings about an increase in the obtained signal in the dielectric loss spectrum, implying that the observed feature of pseudo-dielectric relaxation is actually superposed or contributed by the intrinsic relaxation signal. Furthermore, as temperature continues to rise, the intrinsic dielectric loss signal of NOA65 becomes untraceable beyond the frequency span within which the pseudo-dielectric relaxation signal lies.

Drug-amino acid interaction: Molecular dynamics in aqueous medium using time domain reflectometry

Present work reports dielectric response of the non-steroidal anti-inflammatory drug (NSAID) aceclofenac in aqueous valine solutions at various concentrations and temperatures (278.15 K–298.15 K) in the frequency range of 0.01 GHz to 30 GHz using Time-domain reflectometry (TDR) technique. The frequency dependent complex dielectric permittivity has been analyzed by Harviliak-Negami equation. Debye model is used for the description of complex dielectric permittivity spectra ε*(ν). The structural and dynamical properties of water has been investigated at different concentrations of valine and aceclofenac using dielectric as well as thermodynamic parameters that includes static dielectric constant (ε0), relaxation time (τ0), Kirkwood correlation factor (g), free energy of activation (ΔF), entropy of activation (ΔS), and enthalpy of activation (ΔH). Towards the measured low temperature and high concentrations of Valine and Aceclofenac (ACF), static dielectric constant (ε0) was found to be increasing. This could be due to increased effective dipole-dipole parallel alignment and can be confirmed by the increasing values of correlation factor (g > 1). The dipole-dipole interaction between Drug-Amino acid resulted in increased dielectric relaxation time (τ0) of system due to increased steric hindrance for the rotation of dipoles. The free energy of activation was found to be in the range of 2.22 and 2.58 Kcal mol-1. The entropy is more negative at high concentration suggesting more ordered structure. The slope of log (Tτ0) vs. 1000/T gives the value of enthalpy (ΔH).

Effect of soil compaction on the measurements of complex dielectric permittivity spectrum with an open-ended antenna probe and the coaxial cell system

The paper proposes the use of dielectric spectroscopy to measure changes in dielectric permittivity for soil subjected to compression. Density-dependent dielectric permittivity characteristics of soils for the entire range of obtained density, and thus for a significant parameter of soil properties corresponding with ideal conditions for plant growth as well as those inhibiting their growth were presented. Measurements were carried out for three soil types with different moisture content using an open-ended antenna probe (OE-A), operating in the frequency range of 20 MHz–1.2 GHz and a coaxial cell system in frequency range of 20 MHz–3 GHz. Experimental results showed that an increase in bulk density and volumetric water content of soil affects the complex dielectric permittivity spectrum – a model for this relationship was proposed. Soil dielectric permittivity as a parameter reflecting soil moisture and density can be useful in assessing soil quality.

Geometrical, Electronic, and Optical Properties of Rhombohedral B6O from First‐Principles Calculation

The first‐principles computational methods based on density functional theory are used to study B6O, including its structural, elastic, electronic, and optical properties. The results show that the obtained structural and mechanical parameters are in good agreement with the experimental values. The elastic constants, bulk modulus, shear modulus, Young's modulus, Poisson's ratio, and mechanical stability of rhombohedral B6O are studied. The results show that B6O has mechanical stability, anisotropy, and brittleness. The electronic structure of B6O is analyzed by band structure and density of states. Besides, the chemical bond is systematically explained in terms of Mulliken population and charge density. Finally, the optical characteristics of B6O are examined, encompassing aspects such as the complex dielectric function, conductivity, reflectivity, refractive index, absorption spectrum, and loss function.

Fingerprints of the Jahn-Teller and superexchange physics in optical spectra of manganites

Transition metal oxides incorporating Jahn-Teller (JT) ions Mn3+ (3d 4) in manganites and Cu2+ (3d 9) in cuprates exhibit outstanding magnetic and electronic properties, including colossal magnetoresistance (CMR) and high-temperature superconductivity (HTSC). The physics of these compounds is associated with the orbitally-degenerate electronic states of JT ions, leading to the linear electron-lattice interaction, complemented by the entirely electronic superexchange (SE) interaction. Here, we discuss the fingerprints of the JT and SE physics in the temperature-dependent complex dielectric function spectra and multi-order Raman scattering spectra measured in a detwinned LaMnO3 crystal, which is a famous compound exhibiting cooperative JT effect, being also a progenitor of magnetic materials exhibiting CMR effect. In accordance with the obtained experimental evidence, the associated effective parameters characterizing the JT and SE physics in manganites are presented.

High frequency dielectric study on the hydrogen bonding interaction on 1,5-pentanediol + 1,4-dioxane binary mixtures

The complex dielectric permittivity spectra (CPS) of a binary mixture of 1,5-pentanediol (1,5-PD) with 1,4-dioxane (1,4-DX) were determined using time-domain reflectometry in the frequency range of 10 MHz to 30 GHz. The experimental CPS data were fitted to the Cole–Davidson equation using a nonlinear least squares fit method to determine the dielectric relaxation parameters. The intermolecular interactions in the binary liquids were studied through the Kirkwood correlation factor, excess parameters, thermodynamic parameters, and Bruggeman’s factor.

Magnetic and dielectric properties of Nd-Sn-Cu co-doped yttrium iron garnet ferrite

Ion doping to regulate the magnetic and dielectric properties of yttrium iron garnet ferrites is highly desirable for microwave devices. This study successfully fabricated Y3-xNdxFe4.8Cu0.1Sn0.1O12 (x = 0, 0.5, 1.0, 1.5) ceramics, controlling their magnetic and dielectric properties via Nd ion doping. The results indicate that the introduction of Nd ions into the YIG lattice, occupying dodecahedral sites and replacing Y3+ ions, leads to an increase in the lattice parameter. The hysteresis loops demonstrate that as the concentration of Nd ion doping increases, the saturation magnetization initially decreases and then increases. Additionally, the complex impedance and dielectric spectrum analysis reveal that the resistivity and dielectric constant of the material increase with the increasing concentration of Nd ion doping. The real part of the dielectric constant reaches its maximum value, 29.5@200 kHz, at x = 1.5. Consequently, Nd doping concentration effectively controls the crystal structure, microstructure, magnetic, and dielectric properties of garnet ferrite, enhancing its magnetic and dielectric properties and potential application in microwave devices.

A first-principles investigation on the structural, electronic and optical characteristics of tetragonal compounds XAgO (X = Li, Na, K, Rb)

First-principles calculations employing the density functional theory full-potential (linearized) augmented plane-wave plus local orbitals (FP-(L)/APW + lo) method were conducted to investigate the structural, electronic and optical characteristics of silver-based ternary oxides XAgO (X = Li, Na, K, and Rb). The GGA-PBEsol and TB-mBJ functionals were employed to describe the exchange-correlation potential. The optimized lattice parameters and atomic positions obtained from the calculations exhibit good agreement with both theoretical predictions and experimental measurements. Various exchange-correlation functionals were employed to evaluate the electronic properties, revealing that the newly developed Tran–Blaha modified Becke–Johnson functional yields a significant improvement in the band gap value. All XAgO compounds under consideration are categorized as semiconductor materials where the band gap value decreases as the atomic size of the X element increases. The study also explored the total and site-projected l-decomposed densities of states. Additionally, the complex dielectric function, refractive index, extinction coefficient, reflectivity, and loss function spectra were calculated for the incident radiation polarized parallel to both the [100] and [001] crystalline directions. The interband transitions that contribute effectively to the observed peaks in the imaginary part of the dielectric function were identified.

Fingerprints of Mott–Hubbard physics in optical spectra of antiferromagnetic LaTiO3

Magnetic properties of Mott–Hubbard insulators are determined by superexchange interactions mediated by the high-spin (HS) and low-spin (LS) intersite d–d charge excitations, which can be associated with the HS- and LS-Hubbard subbands in optical experiments. To explore the Mott–Hubbard physics in orthorhombic LaTiO3 crystal exhibiting the G-type antiferromagnetic order at the Néel temperature TN = 146 K, we present a comprehensive spectroscopic ellipsometry study in the spectral range 0.5–5.6 eV at temperatures 10 ⩽ T ⩽ 300 K. We found that the complex dielectric function spectra of LaTiO3 crystal are almost featureless, nearly isotropic, and weakly temperature dependent in the range of the intersite d–d optical transitions. Nonetheless, analyzing the difference spectra below the TN, we have identified the LS-state d1d1⇌d2d0 excitations at ∼3.7 and ∼5.15 eV and estimated values of the on-site Coulomb repulsion U ∼ 4.2 eV and Hund’s exchange constant JH ∼ 0.5 eV, which define the energy of the HS-state d1d1⇌d2d0 excitation at ∼2.7 eV. In addition, we discovered that the pronounced lowest-energy 1.3 eV optical band displays the critical intensity behavior and anomalous broadening with decreasing temperature below the TN. The discovered properties indicate that the 1.3 eV band in LaTiO3 can be associated with a Mott–Hubbard exciton.

Structural and dielectric relaxation studies of 1, 4, and 1, 3 -butanediol–1, 4-dioxane mixtures using TDR technique

Time domain reflectometry (TDR) was used to examine the complex dielectric permitivity spectra (CPS) of binary mixtures of 1,4, and 1,3 butanediol (BD) with 1,4 Dioxane (Dx) at high frequencies (10 MHz–50 GHz). Both systems show the Cole–Davidson type of relaxation process. The least squares fit (LSF) method is applied to compute dielectric relaxation parameters from the CPS. The interest of the ongoing research is to understand the molecular associations, orientation of electric dipoles, and change in electric dipole density in the liquid mixture with the help of excess dielectric parameters, Bruggeman factor (fB) and the Kirkwood correlation factor for both systems.

Pressure-induced metallization in the absence of a structural transition in the layered transition-metal dichalcogenide ZrSe2.

First-principles calculations were carried out on the ZrSe2 compound, which has been of interest owing to its technologically important physical properties. The structural, electronic and optical properties of this compound were investigated under pressure through the plane wave pseudopotential approach within the framework of density functional theory. A comparison between the computed crystal structure parameters and the corresponding experimental counterparts shows a very good agreement between them. Fitting the pressure-volume data using the third-order Birch-Murnaghan equation of state yielded a bulk modulus B0 = 38.17 GPa and a pressure derivative of bulk modulus B'0 = 8.2 for hexagonal ZrSe2. The relationship between the band structure and pressure is revealed. We calculated the total density of state (TDOS) under different pressures and partial density of state (PDOS) from 0 to 10 GPa. According to our calculations, metallization of hexagonal ZrSe2 is predicted to occur at around 10 GPa and pressure-induced band-gap engineering reveals the transformation of the indirect to direct band gap with increasing pressure. Furthermore, optical properties, such as the complex dielectric function, refractive index and reflectivity spectra of this compound, were studied for incident electromagnetic waves in an energy range up to 45 eV. The contributions to various transition peaks in the optical spectra are analyzed and discussed with the help of the energy-dependent imaginary part of the dielectric function.

Study of molecular interactions in aqueous polymer in presence of NSAID using spectroscopic technique

The dielectric study of aqueous Polyvinylpyrrolidone (PVP) (K-30) has been carried out in the presence of Ibuprofen (IBP) in the frequency range of 0.01 GHz – 30 GHz at the temperature 298.15 K using time domain reflectometry (TDR). Harviliak-Negami equation is used for the description of complex dielectric permittivity. The complex dielectric permittivity spectra ε*(ν) is described by using Cole-Cole model. The various dielectric properties i.e., dielectric constantεi, dielectric relaxation timeτi, correlation factor g, effective dipole moment μeff were calculated. Two relaxation processes has been observed namely low frequency relaxation (secondary) and high frequency relaxation (primary) for aqueous PVP-IBP mixture.

Revealing complex relaxation behavior of monohydroxy alcohols in a series of octanol isomers.

We investigate the reorientation dynamics of four octanol isomers with very different characteristics regarding the formation of hydrogen-bonded structures by means of photon-correlation spectroscopy (PCS) and broadband dielectric spectroscopy. PCS is largely insensitive to orientational cross-correlations and straightforwardly probes the α-process dynamics, thus allowing us to disentangle the complex dielectric relaxation spectra. The analysis reveals an additional dielectric relaxation contribution on time scales between the structural α-process and the Debye process. In line with nuclear magnetic resonance results from the literature and recent findings from rheology experiments, we attribute this intermediate contribution to the dielectric signature of the O-H bond reorientation. Due to being incorporated into hydrogen-bonded suprastructures, the O-H bond dynamically decouples from the rest of the molecule. The relative relaxation strength of the resulting intermediate contribution depends on the respective position of the hydroxy group within the molecule and seems to vanish at sufficiently high temperatures, i.e., exactly when the overall tendency to form hydrogen bonded structures decreases. Furthermore, the fact that different octanol isomers share the same dipole density allows us to perform an in-depth analysis of how dipolar cross-correlations appear in dielectric loss spectra. We find that dipolar cross-correlations are not solely manifested by the presence of the slow Debye process but also scale the relaxation strength of the self-correlation contribution depending on the Kirkwood factor.

Water hydration of polyethylene glycol dimethyl ether.

In this work, GHz and THz complex dielectric spectra of a polyethylene glycol dimethyl ether (2000 g/mol) aqueous solution were studied. The reorientation relaxation of water in this kind of macro-amphiphilic molecule solution can be well described by three Debye models, including under-coordinated water, bulk-like water [water molecules in a tetrahedral hydrogen bond network (bulk water) and bulk water molecules affected by hydrophobic groups], and slow hydrating water (water molecules donating hydrogen bonds to hydrophilic ether groups). The reorientation relaxation timescales of bulk-like water and slow hydration water both show increases with concentration from 9.8 to 26.7ps and from 46.9 to 100.1ps, respectively. By estimating the ratios of the dipole moment of slow hydration water to the dipole moment of bulk-like water, we calculated the experimental Kirkwood factors of bulk-like and slow hydrating water. The experimental Kirkwood factor of bulk-like water increased from 3.17 to 3.44 with concentrations, while the experimental Kirkwood factor of slow hydrating water roughly remained constant at 4.13 from concentrations of 15%-60%. The estimated water molecule numbers of three water components around monomers also confirm our sorting for water components.

Size-dependent optical properties of small titanium nitride nanoclusters

The calculation of optical properties of nanoclusters is a challenging and intriguing work. Depending upon the size and shape of the structure, they show some unique behavior. One of the most promising alternative plasmonic materials, titanium nitride has already been explored rigorously in bulk and films in terms of various properties. Here for the first time, the optical property calculation of small titanium nitride nanocluster systems are done using first-principles method. The calculated complex dielectric function, refractive index, extinction coefficient, loss function, reflectivity spectra, and absorption spectra provides information about the response of the clusters to the external field. A significant variation in the optical properties is observed with the change in the cluster size. The tiny size of the clusters is playing a significant role in giving out some fascinating results.

Structural, electrical and leakage current behaviour of double perovskite Gd2NiTiO6

This work discusses the synthesis, characterization, and electrical properties of Gd2NiTiO6 (GNTO) double perovskite synthesized using the sol-gel citrate auto-ignition method. The structure, microstructure, and compositional distribution of the sample were analyzed by X-Ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), and Energy Dispersive X-ray (EDX) analysis. Rietveld's refinement of the XRD pattern corroborated the single-phase monoclinic structure with space group P21/n. The impedance spectra demonstrated grain and grain boundary contributions to the total conductivity and the non-Debye type relaxation. The electrical study also established the semiconductive character of the material. The investigation showed that the conduction mechanism was thermally activated. The frequency-dependent complex dielectric spectra have been investigated using the Havriliak-Nigami (HN) formalism. The temperature variation of leakage-current density was found from J-E characteristics curves.

First-principles Calculations of the Electronic Structure and Optical Properties of Graphene-like InxAl1-xN Monolayers

This paper employs the Heyd-Scuseria-Ernzerhof (HSE) function to research electronic structures of monolayer InxAl1-xN with different compositions (x = 0, 0.25, 0.5, 0.75, 1) based on the first-principles, and the optical properties of single-layer InxAl1-xN are calculated by Generalized Gradient Approximation-Perdew Burke Ernzerhof (GGA-PBE) function. The influence of the electronic structure on the properties has been analyzed. Then the influence of doping quantity on the characteristics has been summarized, which also indicates the trend of the complex dielectric function and absorption spectrum. The calculation results show that with the increase of x, the static dielectric constant increases, the electron transition ability increases, and the absorption peak intensity in the light absorption spectrum increases. It can conclude that the InxAl1-xN compound can theoretically achieve the adjustable Eg and photoelectric performance with x, which will apply in making various optoelectronic devices, including solar cells and sensors.

First-principles calculations to investigate the optoelectronic, and thermoelectric nature of zinc based group II-VI direct band semiconductors

The electronic structure, optical, and thermoelectric properties of novel zinc-based group II-VI semiconductors are investigated using first-principles calculations based on density functional theory. The ternary type materials' structural parameters and electronic band profiles were computed with the advanced TB-mBJ potential. Our computations indicated that the materials are direct band-type semiconductors, with energy gaps of 1.65 eV for MgZnO2 and 2.54 eV for MgZnS2, respectively. If the adjacent valence band is retained, the motion linked with conduction band minima around the Fermi level would most likely reproduce the function in the band gap opening, being the major reason for the decrease in the band gap value from MgZnS2 to MgZnO2. For these materials, the estimated total density of states showed a progressive move along with the energy value. To investigate the optical transitions in these materials, linear optical characteristics such as the complex dielectric function, loss functions, absorption coefficients, reflectivity spectra, and refractive indices were computed and discussed. Furthermore, the thermoelectric properties of these materials were calculated indicating that these materials are competent for applications involving thermoelectric devices.

(Invited) A Formalism Relating the Relative Humidity to the Proton Conductivity Mechanism of Membranes

The relationship between relative humidity of gas phase and proton conductivity in proton exchange membranes has been subject of extensive investigations [1],[2]. Herein, a theoretical framework is presented which describes proton transport in relation to stepwise equilibria that reflect the water uptake. In the proposed model, at first, the hydration process is treated as a stepwise equilibrium process, in agreement with experimental observations. Several hierarchical levels of structure evolve with increasing hydration. These levels are easily confirmed by the analysis of the electric response of perfluorinated based membranes by complex dielectric and conductivity spectra. Thus, a wide range of literature data on hydration of Nafion as a function of activity and temperature has been analyzed by means of the proposed model to extract chemical parameters diagnostic of the type of interactions characterizing the hydrophilic domains of membranes.These parameters, which are crucial in order to modulate the ion transport phenomena in ionomers, are then introduced into the model to describe the functional dependence of conductivity on water activity in gas phase. The treatment of proton conductivity is built on the approaches commonly adopted to describe transport in solids [3]. Key proton migration phenomena appropriate to the levels of the structural hierarchy are considered. The conductivity model is used to describe a set of conductivity vs. water uptake data as a function of temperature, with data taken to exceptionally low water contents. The formalism is then used to analyze a set of data for a perfluorosulfonic acid (PFSA) membrane as a function of hydration, temperature and polymer equivalent weight. The main advantage of the proposed framework is the possibility of a straightforward application to multiple membrane types based on the energetics of water uptake. Actually, the focus on chemical interactions allows to better correlate the effects of the morphology and relaxation events of the matrix to the proton migration phenomena of the membrane. Acknowledgements This work has received funding from: (a) the European Union’s Horizon 2020 research and innovation program under grant agreement 881603; (b) the project ‘Advanced Low-Platinum hierarchical Electrocatalysts for low-T fuel cells’ funded by EIT Raw Materials.