Dielectric relaxation study of dipropylsulfoxide/water mixtures

The complex dielectric spectra of dipropylsulfoxide (DPSO)/water mixtures in the whole concentration range have been measured as a function of frequency between 100 MHz and 20 GHz at four temperatures between 298.15 K and 328.15 K. The dielectric parameters, static dielectric constant (ε_s), relaxation time (τ) and relaxation strength (Δε) have been obtained by the least squares fit method. The relaxation in these mixtures can be described by two Debye functions, whereas for pure DPSO Cole-Davidson type is valid. The relaxation times of the mixtures show a maximum at about x(DPSO) ≈ 0.3. In the concentration range where a maximum appears, the interaction of DPSO with water is presumably the result of hydrogen bonding between water and the sulfonyl group of the sulfoxide molecule. The concentration and temperature dependent excess dielectric constant and effective Kirkwood correlation factor of the binary mixtures have been determined. The excess permittivity is found to be negative for all concentrations.     

Dielectric studies of alkyl acrylates with primary alcohols using time domain reflectometry

Binary polar–polar liquid mixtures of alkyl acrylates (methyl acrylate, ethyl acrylate and butyl acrylate) with primary alcohols (propan-1-ol, butan-1-ol and hexan-1-ol) were subjected to dielectric studies at 303?K for different concentrations using time domain reflectometry (TDR) over the frequency range from 10?MHz to 10?GHz. Static permittivity (ε₀) dielectric constant at high frequency (ε_∞) and relaxation time (τ) were found through dielectric measurements for different concentrations of each system. The Bruggeman dielectric factor, Kirkwood correlation factor and the excess inverse relaxation time were determined and discussed to yield information on the molecular interactions of the systems. Deviations from the linearity of various models suggest molecular association through hydrogen bonding between the ?OH group of alcohols and C=O group of esters. The results also show a dependence of dielectric parameters on the alkyl chain length of both the alcohols and esters.     

Synthesis and spectroscopic investigation of a novel solvatochromic dye

Optical response of a novel dye has been studied in various media like neat and mixed binary solvents, aqueous SDS micelles and β-cyclodextrin (β-CD) nanocavities. Fluorescence parameters in pure and mixed binary solvents have been found to be sensitive to the nature of the microenvironment. The emitting state of the dye in protic solvent is different from that in aprotic solvents. In presence of cations (H⁺, Mg²⁺), the dye exists in two tautomeric forms at equilibrium in solution. The values of the equilibrium constant (K) and ΔH⁰ have been measured. Values of local dielectric constant (ε) and microviscosity (η) at the region of solubilisation of the dye in aqueous SDS micellar media have been found out. The dye has also been found to form complex with β-CD. The equilibrium constant and the energy of maximum fluorescence of the dye encapsulated by β-CD have been determined.     

A comparative study of non-polar solvents effect on dielectric relaxation and dipole moment of binary mixtures of mono alkyl ethers of ethylene glycol and of diethylene glycol with ethyl alcohol

Dielectric relaxation and dipole moment of binary mixtures of homologous series of mono alkyl ethers of ethylene glycol and of diethylene glycol, i.e., mono methyl, mono ethyl and mono butyl ethers of ethylene glycol (ROCH₂CH₂OH) and mono methyl, mono ethyl and mono butyl ethers of diethylene glycol (ROCH₂CH₂OCH₂CH₂OH) with ethyl alcohol (C₂H₅OH) of different concentrations were studied in dilute solutions of benzene, dioxane and carbon tetrachloride at 35 °C. Permittivity (ε′) and loss (ε″) at 10.1 GHz, static dielectric constant ε_o at 1 MHz and high frequency limiting dielectric constant ε_∞ = n_D² at optical frequency of these molecules and their binary mixtures at different concentration were measured in dilute solutions of non-polar solvents. The average relaxation time τ_o, relaxation times corresponding to overall molecular reorientation τ₁ and group rotations τ₂ were determined using Higasi's single frequency measurement equations for dilute solutions. The evaluated values of relaxation times and free energy of activation ΔF were used to explore the solvent effect on molecular dynamics of these polar binary systems in non-polar solvents. The excess inverse relaxation time and excess free energy of activation were determined to confirm the existence of hydrogen-bonded heterogeneous cooperative domains of the ethers and alcohol molecules at different concentration their binary mixtures in non-polar solvents. The dipole moment of the binary mixtures was evaluated using Higasi's and Guggenheim's equation for dilute solutions. The evaluated values of dipole moments and computed dipole moment values using a simple mixing equation of the polar molecules binary mixture were used to explore the effect of non-polar solvent environment on heterogeneous molecular interactions between ethers and alcohol molecules. The effect of number of carbon atoms in the molecular structure of these homologous series molecules was also considered for the interpretation of various evaluated dielectric parameters.     

Photoinduced electron transfer of Rhodamine 6G/N,N-diethylaniline revealed by multiplex transient grating and transient absorption spectroscopies

The dynamics and spectroscopic characteristics of the ultrafast photoinduced electron transfer (ET) of Rhodamine 6G (Rh6G⁺) in N,N-diethylaniline (DEA) were studied using femtosecond time-resolved multiplex transient grating and transient absorption spectroscopies. The ultrafast photoinduced forward ET from DEA to the Rh6G⁺* cation radical excited state has a time constant of τ _FET = 219–318 fs. The much slower backward ET from the neutral radical Rh6G^· to DEA⁺ with a time constant of τ _BET = 22.76–42.31 ps occurs in the inverted region. Intramolecular vibrational relaxation of the excited state takes place in τ _IVR = 2.18–6.91 ps.     

Dielectric parameters in Se70Te30 and Se70Te28Zn2 chalcogenide glasses

Temperature and frequency dependence of dielectric constant (ε′) and dielectric loss (ε″) are studied in glassy Se₇₀Te₃₀ and Se₇₀Te₂₈Zn₂. The measurements have been made in the frequency range (8-500 kHz) and in the temperature range 300 to 350 K. An analysis of the dielectric loss data shows that the Guintini's theory of dielectric dispersion based on two-electron hopping over a potential barrier is applicable in the present case.No dielectric loss peak is observed in glassy Se₇₀Te₃₀. However, such loss peaks exist in the glassy Se₇₀Te₂₈Zn₂ in the above frequency and temperature range. The Cole-Cole diagrams have been used to determine some parameters such as the distribution parameter (α), the macroscopic relaxation time (τ₀), the molecular relaxation time (τ) and the Gibb's free energy for relaxation (ΔF).     

The study of dielectric relaxation and glass forming tendency in Cd-Se-Te glassy system

The dielectric relaxation spectroscopes of Cd_xSe_70−xTe₃₀ (where x = 0, 5, 7, 10) alloy have been investigated in the temperature range 298-373 K and in the frequency range 100 Hz to 100 kHz near the percolation threshold. The frequency and temperature dependence on the dielectric constant showed a Debye dielectric relaxation process. Using Debye relation, the dielectric constant (?′), the most probable relaxation time (τ) and the barrier height (W) were estimated for binary ternary chalcogenide systems.In addition, the analysis of the results suggests that the effect of Cd content on electronic conduction of the system. The experimental results support to some extent the above criterion in the case of Cd-Se-Te ternary alloy.     

Micellar effects on the molecular aggregation and fluorescence properties of benzazole-derived push-pull butadienes

The absorption and fluorescence spectral behaviour of 1-(2-benzoxazolyl)-4-(p-dimethylaminophenyl)buta-1,3-diene and its benzothiazolyl analogue (abbreviated as BODB and BTDB, respectively) have been investigated in dioxane-water mixtures and micellar environments using steady-state techniques. In water, water-rich mixtures or premicellar solutions, BODB and BTDB tend to form molecular aggregates labelled as H-aggregates. These aggregates dissociate on adding surfactants forming micellized monomers. In all micellar media the fluorescence quantum yield is greatly enhanced along with a large hypsochromic shift. Also, in TX-100, CTAB and SDS both dienes show dual emission from the locally excited (LE) and intramolecular charge transfer (ICT) states. For BTDB in TX-100 and DODB in all solutions, the LE fluorescence predominates, while for BTDB in CTAB and SDS, the ICT fluorescence is the predominant. The fluorescence shifts suggest that the fluorescing molecules penetrate the core of the micellar unit in TX-100, whereas in CTAB and SDS they occupy the interfacial region. The binding constants and the micelle properties (such as polarity and CMC) have been determined using both dienes as probes.     

Dielectric dispersion studies of aromatic ketones in non-polar solvents

Measurements of dielectric constant (ε′) and loss (ε″) have been made at five different microwave frequencies from 1000 MHz to 67.7 GHz for acetophenone, benzophenone and propiophenone in four different non-polar solvents namely benzene, cyclohexane, 1-4-dioxane and n-heptane. Results are reported at five different temperatures from 25°C to 60°C. The dielectric data of these ketones in different solvents are analysed in terms of the Cole-Cole arc plots and superposition of two Debye-type absorptions. Values of mean relaxation times (τ_o), dipolement (μ), overall relaxation time (τ₁) and group relaxation time (τ₂) have been obtained and presented here. The values of relaxation time and dipolemoment are in reasonable good agreement, at the temperatures, at which there are available known data.     

Gaussian distribution of relaxation through human blood

The complicated structure of human blood has been characterized based on relaxation time, τ, and the Cole-Cole parameter, α, obtained from dielectric measurements. As previously reported by different authors, the experimental data show net deviation from the classical Debye model with certain distribution of relaxation times (D_τ). Plots of α versus width of the relaxation rate distribution of micro-particles inside the blood show that D_τ drastically affects the dielectric properties of the fluid. The mathematical function of D_τ is found to be Gaussian and we find that the α values of normal blood have net lower magnitude than that of diabetic blood. These results suggest that glucose in blood increases the broadness of the parameter α, which have significant importance in diabetic-biosensor manufacture.     

Structural and AC conductivity study of CdTe nanomaterials

Cadmium telluride (CdTe) nanomaterials have been synthesized by soft chemical route using mercapto ethanol as a capping agent. Crystallization temperature of the sample is investigated using differential scanning calorimeter. X-ray diffraction and transmission electron microscope measurements show that the prepared sample belongs to cubic structure with the average particle size of 20 nm. Impedance spectroscopy is applied to investigate the dielectric relaxation of the sample in a temperature range from 313 to 593 K and in a frequency range from 42 Hz to 1.1 MHz. The complex impedance plane plot has been analyzed by an equivalent circuit consisting of two serially connected R-CPE units, each containing a resistance (R) and a constant phase element (CPE). Dielectric relaxation peaks are observed in the imaginary parts of the spectra. The frequency dependence of real and imaginary parts of dielectric permittivity is analyzed using modified Cole–Cole equation. The temperature dependence relaxation time is found to obey the Arrhenius law having activation energy ~0.704 eV. The frequency dependent conductivity spectra are found to follow the power law. The frequency dependence ac conductivity is analyzed by power law.     

Photophysical properties of a surfactive long-chain styryl merocyanine dye as fluorescent probe

This work deals with detailed investigations of the photophysical properties of a styryl merocyanine dye, namely 1-cetyl-4-[4′-(methoxy) styryl]-pyridinium bromide (CMSPB) of molecular rotor type. The solvatochromic analyses of the data in different solvents using the Kamlet-Taft parameters (α, β, π^?) were discussed. Optical excitation of the studied merocyanine dye populates a CT S₁ state with about 22.64 folds higher dipole moment value relative to that in the S₀ state. Moreover, the effect of solvent viscosity (glycerol at various temperatures (299.0–351.0 K)) on CMSPB fluorescent properties is analyzed to understand the molecular mechanisms of the characteristic increase in CMSPB fluorescence intensity. The results indicate that CMSPB exhibits fluorescent properties typical for molecular rotors. The results show that torsional relaxation dynamics of molecular rotors in high-viscosity solvents cannot be described by the simple stick boundary hydrodynamics defined by the Debye–Stokes–Einstein (DSE) equation. The fluorescence depolarization behavior in glycerol at various temperatures (299.0–351.0 K) shows that the molecular rotational diffusion is controlled by the free volume of the medium. Furthermore, excited state studies in ethanol/chloroform mixture revealed the formation of weak complex with chloroform of stoichiometry 1:1 with formation constant of 0.004l mol^?1. Moreover, the increase of the quantum yield values in micellar solutions of CTAB and SDS relative to that of water indicates that the guest dye molecules are microencapsulated into the hydrophobic interior of host micelle. The obtained non-zero values of fluorescence polarization in micellar solution imply reduced rotational depolarization of dye molecules via association with the surfactant. Upon comparing the spectral data in micelles with those in homogeneous solvent systems, more can be learned of the structural details of the micellar environment, which have often been used as models for more complex bioaggregates. The results point out to a possible use of this dye as a fluorescence probe for microenvironmental parameters as well as in some micellar systems.     

Analysis of Experimental Results by the Havriliak–Negami Model in Dielectric Spectroscopy

The problem of identifying experimental results on studying frequency dependences of the real and imaginary parts of dielectric permittivity concerning the correspondence to one of accepted frequency dispersion models: Debye, Cole–Cole, Davidson–Cole, and Havriliak–Negami models is considered. Based on expressions for components of complex dielectric permittivity with the use of mathematical analysis, a sequence of steps for the determination of the following characteristic parameters of the generalized Havriliak–Negami model is developed: static ε _S and high-frequency ε_∞ dielectric permittivity, frequency dispersion indices α and β, and relaxation time τ. As an example, the parameters ε _S , ε_∞, α, β, and τ are calculated for a sample of a frozen disperse medium based on fine-grained quartz powder at a humidity of 13% in a temperature range from –140 to 0°C.     

Physical mechanisms responsible for the relaxation time distribution in disordered dielectrics

The relaxation time distribution function F(τ) is calculated in the framework of the random-field theory. The function F(τ) is expressed through the distribution function f(E) of a random electric field E with due regard for the derived dependence of the relaxation time τ on the electric field. The distribution function F(τ) is calculated in terms of the statistical theory within the random-field approximation. The nonlinear random-field contributions and spatial effects of correlations between randomly distributed electric dipoles are taken into account. The calculations are performed for a mixed ferroelectric glassy phase in which the short-range and long-range polar orders coexist. It is demonstrated that the inclusion of nonlinear contributions of the random field leads to an asymmetric relaxation time distribution function F(τ), whereas allowance made only for the linear random-field contributions results in a symmetric function F(τ). A comparison of the calculated functions F(τ) with empirical functions derived from the Cole-Cole (CC), Davidson-Cole (DC), Kohlrausch-Williams-Watts (KWW), and Havriliak-Negami (HN) laws for the dielectric response shows that these laws correspond to disordered systems in which the long-range and short-range orders coexist. Different forms of the function F(τ) are determined by either linear (the CC law) or nonlinear (the DC, KWW, and HN laws) contributions of the random field.     

Dielectric dispersion studies of mixtures of aniline and benzonitrile in benzene solutions

Dielectric behavior of aniline, benzonitrile and their binary mixtures of different concentrations were studied in benzene at 293, 303, 313 and 323 K. The complex permittivity (∈′, ∈″) at microwave frequencies 7.22, 9.1, 19.61 GHz, static permittivity ∈₀ at 455 KHz and high frequency limiting dielectric constant ∈_∞ = n_D² at optical frequency of these molecules and their binary mixtures were measured. The average relaxation time (τ₀), distribution parameter (α) and thermodynamical parameters were determined. The plot of relaxation time (τ₀) against concentration of benzonitrile in the mixtures is nonlinear indicating complex formation.     

The dielectric relaxation study of 2(2-alkoxyethoxy)ethanol-water mixtures using time domain reflectometry

Complex permittivity spectra of 2(2-alkoxyethoxy)ethanol-water mixtures for the entire concentration range and at 25 °C have been measured using time domain reflectometry technique up to 30 GHz. The relaxation processes have been obtained by fitting the complex permittivity spectra of the binary mixtures in 2-Debye equation. In glycol ether-water mixtures except for pure water and its rich region the double relaxation times, primary process (τ₁) and secondary process (τ₂) have been observed. The primary relaxation process (τ₁) may be due to cooperative relaxation of the H-bond network of mixture constituents and the secondary relaxation process (τ₂) may be due to its flexible parts attached to the carbon chain. The intra and intermolecular hydrogen bonding of 2(2-alkoxyethoxy)ethanol in pure form as well as in binary mixtures of water have been discussed using Kirkwood correlation factor, Excess dielectric properties and the Bruggeman factor.     

Multicomponent Rayleigh scattering from guanidine hydrochloride solutions

We present results of Brillouin light scattering studies of lysozyme and guanidine hydrochloride solutions in the temperature range 290–350 K. The Brillouin spectra of 6 M guanidine hydrochloride have been found to contain an additional component in Rayleigh scattering that manifests itself as a broad quasi‐elastic scattering line centered at the unshifted frequency and described by a Lorentz function (i.e. a Debye relaxor with relaxation time τ₁ ~ 25 ps at room temperature). The temperature dependence of τ₁ is described by the Arrhenius law with activation energy E_a = 0.11 ± 0.01 eV and prefactor τ₀= 0.33 ± 0.03 ps. The Brillouin spectra of lysozyme denatured by 6 M guanidine hydrochloride exhibit a more complicated structure of the additional contribution into Rayleigh scattering, which is fitted best of all by a sum of two Lorentzians centered at the unshifted frequency (with relaxation times τ₁ ~ 19 ps and τ₂ ~ 180 ps at 339 K). Possible origins of the quasi‐elastic scattering are discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

The Effect of Supercritical CO2 on the Macromolecules Parallel Conformation and Its Relation to the Electrical Conductivity and Dielectric Behavior of Epichlorohydrin Terpolymer

The effect of supercritical CO₂ on the electrical conductivity of poly(epichlorohydrin–Ethylene oxide–Allyl glycidal ether) terpolymer is investigated using dielectric spectroscopy. Impedance measurements were carried out in the frequency range from 100–10 MHz and the temperature range of ?35–70°C with intervals of 5°C. The experimental results of the dielectric constant and the dielectric loss were fitted with the Cole–Cole equation to obtain the maximum relaxation frequencies of the different relaxation processes. As a result of the CO₂ treatment process, enhancement in the polymer chain mobility without noteworthy change in the glass transition temperature was determined. In addition, the level of the DC conductivity and the dielectric strength were increased. These effects were attributed to improvement in the chain dynamics, which arises from enhancement in the parallel conformation of macromolecules.     

Possible evidence for the relaxation case in CdS

Possible evidence for the effects characteristic of the relaxation case (in which the dielectric relaxation time τ_d=ε? exceeds the minority carrier diffusion length life time τ₀) was observed by photoconductivity experiment in InCdSIn structure. A deviation from linearity in the relationship between conductivity (σ - σ₀) and light intensity (I) is consistent with an analysis based on the theory of relaxation case semiconductor.     

Proton spin-lattice relaxation in liquid water and liquid ammonia

The proton spin-lattice relaxation time has been measured at 20·8 Mc/s for a series of solutions of water in heavy water and solutions of ammonia in heavy ammonia for the temperature range from the melting point to the liquid-vapour critical temperature. Measurements have also been made for water over limited temperature ranges at several fixed densities.

The contributions to the spin-lattice relaxation time from direct dipolar and spin-rotation interactions have been separated. The spin-rotation interaction contribution appears to be the same for H₂O as for HDO and also as between NH₃, NH₂D and NHD₂ and this result is justified. The correlation times for molecular re-orientation, τ_d, and for molecular angular velocity, τ_sr, are derived from the results and in so doing some support for the Hubbard [12] relation betweent τ_sr and τ_d is adduced. It is found that at the critical temperature τ_sr?τ_d which contrasts with other liquids for which it is usually found that τ_sr??τ_d. The spin-rotation interaction constants in the water and ammonia molecules are found to be approximately 120 kc/s and 80 kc/s, respectively.

An attempt to separate the inter- and intra-molecular contributions to the dipolar spin-lattice relaxation time is possible in principle, in spite of the rapid proton exchange, but is frustrated by the fact that the equilibrium constants are little different from their statistical values. Nevertheless there is evidence that the two interactions vary in much the same way with temperature.

The correlation times deduced from the dipolar relaxation time show close relationship with dielectric, self diffusion and deuteron relaxation time data.

It is suggested that the re-orientation of both water and ammonia molecules may be by a small angle Brownian diffusion even near the critical temperature.