Study of activation parameters and NMR spin-lattice relaxation time in some substituted amines

The present communication reports the experimental values of NMR spin-lattice relaxation time (T₁) and dielectric relaxation time (τ) of piperidine, pyrrole, pyridine, diethylamine, triethylamine and pyrrolidine. The values of activation energy (ΔE_A) obtained using dielectric relaxation time, have been correlated with calculated values of ΔE_A obtained using Arrhenius equation of NMR relaxation time (T₁) for pyridine, diethylamine and pyrrole. Authors have also established a correlation between the experimental values of NMR spin-relaxation time (T₁) with its calculated values obtained using different equations of dielectric relaxation time (τ).     

Effect of the dielectric background on dispersion characteristics of metallo-dielectric photonic crystals

We theoretically study the effect of the dielectric background in two-dimensional metallo-dielectric photonic crystals. The metallo-dielectric photonic crystal consists of a square lattice of circular metallic rods embedded into a dielectric background. We calculate the photonic band structure by means of the plane wave method and the frequency-dependent finite-difference time-domain method. The transfer matrix method is used to obtain the reflectivity characteristics. Results show that the band structures shift toward lower frequencies and become flatter when the background dielectric constant increases. In addition, degeneracy can be broken and new gaps can be created in function of the dielectric background. We also found that the relative band gap width Δω/ω_g grows with increasing background dielectric constant and widths as large as 42.3% and 13.8% for the second and third band gaps can be achieved for ε_b = 9. We have investigated the origin of the new gap in these structures by studying the electric-field distribution at the band edges for the first five modes.     

Pressure–temperature studies on conductivity of TlX(X=Cl,Br,I) compounds:: I: phase diagram. II: ionic mobility

We have measured the conductivity σ of TlX(X=Cl, Br, I) compounds up to 5.3 GPa and between 300–823 K. The σ–T dependence for all compounds can be divided into three distinct regions: (i) low temperature (LT), <400 K, with unusual negative σ–T dependence, (ii) intermediate temperature (IT), 400<650 K, with positive σ–T dependence and (iii) high temperature (HT), T>650 K, with positive σ–T dependence. The σ–T isobars were used to construct the T–P solid phase diagram for each compound. The LT region data indicate a new meta-stable phase in the 1.0–3.5 GPa range. The LT→IT transition is characterized by an inverse σ–T dependence followed by normal Arrhenius behavior up to and including the HT region. The extrapolation to 1 atm of the P-dependent boundary between IT and HT regions above 3 GPa for each compound in the P–T plot yields a value close to its respective normal (1 atm) T_melt suggesting a solid order–disorder transition type paralleling -AgI behavior. The abrupt drop in conductivity in the LT region for P between 2.5–4.1 GPa of all compounds is at variance with the Arrhenius behavior observed for unperturbed ion migration implying the appearance of a second factor overriding the Arrhenius temperature dependence. Normal Arrhenius σ–T dependence prevails in both IT and HT regions with Q_c values of 85–100 kJ mol⁻¹ and 50–75 kJ mol⁻¹, respectively. The higher conductivities at 0.4 GPa for TlBr and TlI relative to their 1 atm data and the increasing σ with P are in strong contrast to the normal σ-P behavior of TlCl. The dependence of activation volume ΔV^‡ on T for TlCl, i.e. ΔV^‡>0, shows abnormally high values with a maximum at 500 K for P<3.0 GPa but reasonable ΔV^‡ values appear above 3.0 GPa. The ΔV^‡–T dependence for both TlBr and TlI with ΔV^‡<0 is incompatible with an ion transport mechanism suggesting an electronic conduction process and implying an ionic–metallic transition at higher pressures. These contrasting conductivity features are discussed and interpreted in terms of electronegativity differences and bonding character rather than structure.     

Dielectric and modulus behavior of LiFe1/2Ni1/2VO4 ceramics

The polycrystalline sample of LiFe_1/2Ni_1/2VO₄ was prepared by a standard solid-state reaction technique and confirmed by X-ray diffractometry. LiFe_1/2Ni_1/2VO₄ has orthorhombic crystal structure whose dielectric and electric modulus properties were studied over a wide frequency range (100 Hz–1 MHz) at different temperatures (296–623 K) using a complex impedance spectroscopy (CIS) technique. The frequency and temperature dependence of dielectric constant (ε_r) and tangent loss (tan δ) of LiFe_1/2Ni_1/2VO₄ are studied. The variation of ε_r as a function frequency at different temperatures exhibits a dispersive behavior at low frequencies. The variation of the ε_r as a function of temperature at different frequencies shows the dielectric anomaly in ε_r at 498 K with maximum value of dielectric constant 274.49 and 96.86 at 100 kHz and 1 MHz, respectively. Modulus analysis was carried out to understand the mechanism of the electrical transport process, which indicates the non-exponential type of conductivity relaxation in the material. The activation energy calculated from electric modulus spectra is 0.38 eV.     

Dynamical spin susceptibility of the d–p model in the over doping region

Dynamical spin susceptibility χ^s(q,ω) of the d–p model in the over doping region is investigated by using the auxiliary boson technique. It includes higher order terms of the 1/N-expansion within the random phase approximation (RPA) of the local vertex, where frequency dependence of the quasi-particle interaction is taken into account. The incommensurate spin fluctuation is obtained due to the nesting effect in the low energy region (ωω^*), whereas the commensurate one in the high energy region (ωω^*), the characteristic energy ω^* is estimated to be about 30 meV. Both of the spin–lattice relaxation rate 1/T₁ and the spin–spin relaxation rate 1/T_g monotonically increase as T decreases, while the spin Knight shift K is almost independent of T.     

Methods for correlating T1rho and FID components in wideline 1H NMR studies of motionally heterogeneous polymer systems

We address the problem of correlating the observed FID and T_1ρ components in wideline ¹H relaxation measurements of motionally heterogeneous polymers, and show that different methods of data treatment can highlight different aspects of the correlations present. For a sample of polypropylene we find that the T_1ρ relaxation behaviour is driven by relaxation associated with the intermediate FID component, which strongly suggests a motionally inhomogeneous amorphous region in the sample.     

Resolution of conflicting views concerning frequency-response models for conducting materials with dispersive relaxation, and isomorphism of macroscopic and microscopic models

Possible errors in the widely used 1972–1973 macroscopic original-electric-modulus formalism are identified, corrected, and their consequences considered. These errors include misidentification of the high-frequency-limiting dielectric constant arising entirely from mobile charges, ε_C1∞, and the failure to treat properly the high-frequency-limiting dielectric constant associated with bulk dipolar and vibrionic effects, ε_D∞. It is shown that the corrected modulus formalism, which describes dispersed mobile-charge effects, is isomorphic in form with the 1973 microscopic continuous-time random-walk hopping model of Scher and Lax after a minor but significant correction is made to the latter's response function. This firmly established correction, which nevertheless could not be determined by Kronig–Kramers transformation, involved inversion of synthetic frequency-response data to determine a distribution of relaxation times and led to extension of the real part of the Scher–Lax dielectric response to higher frequencies by the inclusion of a nonzero limiting value. This isomorphism, along with excellent data fitting using the corrected modulus formalism, suggests that since the Scher–Lax stochastic model involves no explicit Coulomb interactions, cation motion in glasses is dominated by short-range interactions. Finally, two very-high-frequency processes, which each lead to a limiting plateau value of the real part of the conductivity at sufficiently high frequencies, are discussed in detail.     

Rotational, internal rotational, and translational motion of acetic acid and dimethyl sulfoxide in their liquid mixture (with some results for DMSO dissolved in MeOH)

The proton magnetic relaxation rate of DMSO in the mixture 33.3 mole % DMSO + 66.7 mole % CD₃COOD has been measured in the temperature range 3.5 < 1000/T < 6.0 K and at six frequencies 6 < ν < 144 MHz. The intramolecular relaxation rate was determined by the aid of the isotopic substitution technique. The rotational correlation time of “the molecule” and the time constant of the internal motion have been extracted from these experimental results. The corresponding measurements were also performed on DMSO in the solvent CD₃OD (71 mole %) where no internal motion effect appeared in the temperature dependence of the relaxation rate. Furthermore, proton relaxation rates of the acetic acid methyl group and deuteron relaxation rates of the acid methyl and OD group are reported. Again, the data are given in the temperature range as above and for a number of frequencies. Rotational time correlation functions g(t) for the axid molecule are derived. Finally we present experimental results for the self-diffusion coefficients of both mixture partners DMSO and AcH and of DMSO in the solvent MeOH.     

Structure of some liquid alcohols, diols and triols: an analysis of dielectric data

This work is a continuation of our studies of the liquid structure of polyhydric alcohols and their solutions. Dielectric parameters (relaxation time, average cluster dipole moment μ¯_c, etc.) have been calculated for 1-hexanol in a wide temperature range in the framework of the cluster model proposed by Dissado and Hill; the values of apparent activation enthalpy ΔH_DHexp^≠ have been evaluated. These data were compared with the parameters previously determined by us for 2,5-hexanediol and 1,2,6-hexanetriol; the ratio μ¯_c/μ¯_v was used for an estimation of the number of molecules in clusters. It was found that at all temperatures in the range 303–393 K, the μ¯_c/μ¯_v values for 1-hexanol are significantly larger than the values of average degree of association p¯ calculated from equilibrium dielectric data; the ΔH_DHexp^≠ values for 1-hexanol are considerably lower than those for 2,5-hexanediol and 1,2,6-hexanetriol.     

Dielectric behavior of hexaferrites BaCo2−xZnxFe16O27

The dielectric constant (′) and dielectric loss (tan δ) for hexaferrites BaCo_2−xZn_xFe₁₆O₂₇ have been studied as a function of frequency (f), temperature (T) and composition (x). The experimental results indicate that ′ and tan δ above the relaxation frequency only decrease as the frequency increases and as the temperature decreases. Tan δ shows the dielectric relaxation at certain critical frequencies which rise as temperature increases. The activation energy for the dielectric relaxation (E_D), ′, and tan δ are found to be minimum for x = 0.8.     

Molecular associations in binary mixtures of pyridine and chlorobenzene in benzene solution using microwave absorption data

The dielectric relaxation time (τ) of binary mixtures of different molar concentrations of pyridine (C₅H₅N) and chlorobenzene (C₆H₅Cl) in benzene solution at different temperatures (25, 30, 35 and 40 °C) has been calculated by using standard microwave techniques and Gopala Krishna's single frequency (9.875 GHz) concentration variation method. The energy parameters (ΔH_ε, ΔF_ε, and ΔS_ε) for the dielectric relaxation process of the binary mixture containing 0.5 mol fraction of pyridine have been calculated at the respective temperatures. Comparisons have been made with the corresponding energy parameters for the viscous flow (ΔH_η, ΔF_η, and ΔS_η). From the observations it is found that the dielectric relaxation process can be treated as the rate process. Based upon above studies, solute–solvent type of molecular associations arising from the interaction of chlorobenzene and benzene and pyridine and benzene molecules has been proposed. No solute–solute type of molecular association has been observed.     

On the “quantum rainbow” in surface scattering

In this letter we propose a new method to compute the scattering amplitudes of atoms from a corrugated wall model of a crystal surface. The method method requires reasonable computing time and converges rapidly to the solution of the scattering amplitudes (within 0.01% in each beam and satisfying unitarity) for any corrugation such that kζ₀ < 4.5 and ζ₀ < 0.35 Å, where k is the magnitude of the incident wave vector and ζ₀ the amplitude of the corrugation. These conditions for kζ₀ and ζ₀ are satisfied for any crystal surface and light scattering atoms (H and He) at thermal energies which makes the method appropriate for the system He, LiF for which results are presented comparing them with recent experimental data.     

The electrical impedance,AC conductivity and dielectric properties of phenol red compound investigated and modeled by an artificial neural network

The impedance spectroscopy, electrical conductivity and electric modulus of bulk phenol red were measured, as a function of both frequency and temperature. Artificial neural networks (ANNs) were used for modeling its electrical properties. The two parts (real and imaginary) of its complex impedance (Z*) were analyzed and the activation energy related to the electrical relaxation process was evaluated. Nyquist curves were plotted showing semicircles for the different temperatures. The AC electrical conductivity follows a power law σ_ac(ω) α ω^η. The maximum barrier height B_m was derived for specific temperatures. A plausible mechanism for the AC conduction of bulk phenol red was deduced from the temperature reliance of the frequency exponent. The dielectric data was analyzed using electric modulus as a tool. In addition, ANNs were used to model the impedance parts and the total electrical conductivity. Numerous runs were tried, to obtain the best performance. The training and prediction results were compared to the equivalent experimental results, with a good match obtained. An equation describing the experimental results was obtained mathematically, based on the use of ANNs. The outputs demonstrated that ANNs are an admirable tool for modeling experimental results.     

Characterization of heterogeneous interaction in binary mixtures of ethylene glycol oligomer with water, ethyl alcohol and dioxane by dielectric analysis

The associating behaviour of the binary mixtures of ethylene glycol oligomer (EGO), i.e. ethylene glycol (EG), diethylene glycol (DEG) and poly(ethylene glycol)s (PEG200, PEG300, PEG400 and PEG600) with water (W), ethyl alcohol (EA) and 1,4-dioxane (DX) over the entire concentration range at 25 °C have been investigated through their accurately measured values of dielectric constant. The static dielectric constant ε_o, high frequency limiting dielectric constant ε_∞, dielectric relaxation strength Δε, excess dielectric parameters ε^E₀ and ε^E_∞, effective Kirkwood correlation factor g^eff and corrective correlation factor g_f of EGO–W, EGO–EA and EGO–DX mixtures were determined to obtain qualitative and quantitative information about the complex formation through H-bond in these systems. Most of the evaluated dielectric parameters of EG and DEG in different ‘cosolvents’ have different characteristics as compared to the PEG–cosolvent mixture. The observed linear and non-linear behaviour of Δε against EGO monomer unit mole fraction X confirms the variation in the homogeneous structures in their binary mixtures with concentration variation. Appearance of the maximum in ε^E₀ against X plots indicates that a complex stable adduct is formed in the EGO–W mixtures at stoichiometric ratio 1:1.7 for lower oligomers but this ratio seems to be 1.7:1 for higher EGO molecules, which confirms that the EGO size and chain flexibility affects the complex formation between EGO and W. In case of EG–EA mixture 1:1 stoichiometric ratio form stable adduct whereas for higher EGO–EA, it is 3:1, at EGO monomer unit level. The complex formation behaviour of DEG–EA has entirely different characteristics when compared to the other studied EGO–EA mixtures. Although, 1,4-dioxane has weak polar behaviour dielectric properties of EG–DX and DEG–DX confirm the formation of stable adducts at the stoichiometric ratio 2:1 of EGO monomer unit mole fraction to the DX. For the higher EGO–DX mixtures, stable adduct forms at the stoichiometric ratio 9:1. Except DEG–EA mixtures, the EGO–W and EGO–EA form the complex with reduction in the effective number of dipoles. In EG–DX mixtures, the heterogeneous species form with a large reduction in the effective number of dipoles, which changes as the effective number of dipoles increases with the increase in monomer repeat units of EGO. Further the net electronic polarization in these binary mixtures increases due to heterogeneous interaction over the entire mixing concentration range.     

Adiabatic small polaron-hopping conduction in Ln0.85Ca0.15MnO3 (Ln=Nd, Pr and Sm) perovskites

Polycrystalline bulk ferromagnetic insulating (FMI) Ln_0.85Ca_0.15MnO₃ (Ln=Nd, Pr and Sm) samples are prepared by standard solid-state reaction route and characterized. Powder X-ray diffraction (XRD) data of the manganites show single-phase character. Existing theoretical models predict that the high temperature (T>θ_D/2, θ_D being the Debye temperature) dc conductivity (σ_dc) of these samples is due to adiabatic small polaron-hopping conduction. Greaves’ and Mott's variable range hopping (VRH) conduction mechanisms are not suitable to explain the σ_dc data at low temperature (T<θ_D/2).     

Spin diffusion and nuclear spin-lattice relaxation in irradiated solids: a multiple-pulse NQR study

We present a detailed theoretical and experimental NQR multiple-pulse spin-locking study of spin-lattice relaxation and spin diffusion processes in the presence of paramagnetic impurities in solids. The relaxation function of the nuclear spin system at the beginning of the relaxation process is given by exp , where T_1ρ is spin-lattice relaxation time in rotating frame and =d/6, d is the sample dimensionality. Then the relaxation proceeds asymptotically to an exponential function of time, which was attributed to the spin-diffusion regime. Using the experimental data obtained from the analysis of those two relaxation regimes in γ-irradiated powdered NaClO₃, spin diffusion coefficient has been determined and the radius of the diffusion barrier has been estimated.     

Strain relaxation and surface morphology of high indium content InAlAs metamorphic buffers with reverse step

Low-temperature step-graded high indium content InAlAs (In% = 0.75) metamorphic buffer layers with reverse step layer grown on GaAs substrate by molecular beam epitaxy are investigated in this paper. The composition and the strain relaxation of the top InAlAs layer are determined by high-resolution triple-axis X-ray diffraction measurements, which show that the top InAlAs layer is nearly fully relaxed and the growth parameters for these samples have little influence on the strain relaxation ratio. Surface morphology is observed by reflection high-energy electron diffraction pattern and atomic force microscopy. The surface morphology is found to depend strongly on both the growth temperature and the As flux. Compared with other samples, the sample growth under the optimized conditions has the smallest value of root mean square surface roughness. Furthermore, the ω − 2θ and ω scans of the triple-axis X-ray diffraction and transmission electron microscopy result also show the sample grown under the optimized conditions has good crystalline quality.     

Temperature dependence of the dielectric properties of SBN in the frequency range of 10kHz–10MHz

The dielectric constant of Sr_0.75 Ba_0.25 Nb₂O₆ and its dielectric loss have been measured from -20°C to +90°C at various frequencies in the range of 10 KHz– 10 MHz. The result show, that despite the low half-wave field distance product (E·l)λ/2, the use for light modulation purposes is limited because of the high value of tan σ.