Measurements on polar liquids at a microwave frequency — evaluation of molecular parameters — a new method

A simple method of estimating the dipole moment (μ) and relaxation time (τ) of polar molecules in liquid state, from a single set of dielectric measurements at high frequency, is proposed by using the concept of dielectric virial coefficients and employing Onsager model. The proposed method is tested in a number of polar liquids and the results are discussed.     

Applications of the expanded basis method to study the properties of photonic crystals with frequency-dependent dielectric functions and dielectric losses

Band structures of two-dimensional photonic crystals (PCs) made of polar material with frequency-dependent dielectric constant are calculated by using an expanded basis method. The effect of the polariton gap (PG) of polar material on the photonic band gaps (PBGs) is explored. It is found that the PBGs are significantly modified near the PG, where the abrupt change of the dielectric constant appears. The feature of electromagnetic (EM) field is revealed when the frequency is located in the flat band. We display the equifrequency-surface configuration of the localized field and the spacial distributions of field. We observe the existence of several equi-ω curves for a specified frequency and the localized field distribution exhibiting various different patterns, dependent of the mode index. We also study the influence of the dielectric losses of the polar material on dispersion and find that the change of the real part of the Bloch wave vector is crucially related to the real part of the dielectric constant and the attenuated length is determined by its imaginary part.     

Energy relaxation of hot carriers in single-wall carbon nanotubes by surface optical phonons of the substrate

A new mechanism is proposed for the energy relaxation of hot carriers in single-wall carbon nanotubes: scattering with the emission of surface optical phonons into the semiconductor substrate. The theory involves intrasubband and intersubband forward and backward scattering. The analytical result and numerical data indicate that intrasubband forward scattering is the main process: the corresponding lifetime comprises several femtoseconds for a quartz substrate, which allows this mechanism of energy relaxation to be considered dominating for a nanotube on the surface of a polar semiconductor or a dielectric.     

Photon-counting technique for rapid fluorescence-decay measurement

We report on a novel laser-induced fluorescence triple-integration method (LIFTIME) that is capable of making rapid, continuous fluorescence lifetime measurements by a unique photon-counting technique. The LIFTIME has been convolved with picosecond time-resolved laser-induced fluorescence, which employs a high-repetition-rate mode-locked laser, permitting the eventual monitoring of instantaneous species concentrations in turbulent flames. We verify the technique by application of the LIFTIME to two known fluorescence media, diphenyloxazole (PPO) and quinine sulfate monohydrate (QSM). PPO has a fluorescence lifetime of 1.28 ns, whereas QSM has a fluorescence lifetime that can be varied from 1.0 to 3.0 ns. From these liquid samples we demonstrate that fluorescence lifetime can currently be monitored at a sampling rate of up to 500 Hz with less than 10% uncertainty (1sigma) .     

Dynamics in Diether Lipid Bilayers and Interdigitated Bilayer Structures Studied by Time-Resolved Emission Spectra, Decay Time and Anisotropy Profiles

We present a comparative fluorescence spectroscopic investigation of diacyl and diether phosphatidylcholine vesicles using different probes with well-defined localization within either the hydrophilic headgroup region or the hydrophobic part of the bilayer. Time-resolved emission spectra have been used to characterize the solvent relaxation behavior in both symmetric and asymmetric diether and diacyl phosphatidylcholines. It is shown that time-resolved emission spectra of Prodan (6-propionyl-2-(dimethylamino)-naphthalene) and its long-alkyl chain derivative Patman (6-palmitoyl-2-[[trimethylammoniumethyl]methylamino]-naphthalene chloride) are a sensitive tool for the detection of differences in the micropolarities and viscosities at the hydrophobic/hydrophilic membrane interface of diether and diacyl lipids, respectively. Moreover, a new approach for the detection of interdigitated bilayers is discussed. It relies on the construction of anisotropy and decay time profiles for the set of n-anthroyloxy fatty acids and is compared with an older fluorescence assay based on intensity measurements only. The shape of plots of the fluorescence steady-state anisotropy versus the position of the chromophore (anthracene-9-carboxylic acid) combined with fluorescence lifetime measurements can be used to differentiate among non-fully, and mixed interdigitated gel phase structures and to predict structures for new lipid species.     

Dielectric behaviour of propylene glycol-water mixtures studied by time domain reflectometry

Dielectric relaxation measurements on water mixtures of propylene glycol across the entire concentration range were carried out using time domain reflectometry at 25°C over the frequency range from 10 MHz to 4 GHz. For all the mixtures, only one dielectric loss peak was observed in this frequency range. The relaxation in these mixtures can be described by a single relaxation time using the Debye model. A plot of the calculated relaxation time of the mixtures gives a straight line against the mole fraction of water, X_w. It is reasoned that the diameter of the water cluster is nearly the same as the length of propylene glycol. Further, a plot of the dielectric relaxation strength δ? against X_w suggests that there is a changing pattern of dielectric behaviour from below X_w = 0.5 to higher values of X_w. The excess permittivity, the excess inverse relaxation time and the activation free energy have been determined, to confirm the formation of hydrogen bonded homogeneous and heterogeneous cooperative domains, the dynamics of solute-solvent interaction and the hindrance to molecular rotation in the hydrogen bonded glass forming propylene glycol-water system.     

Spectral densities and nuclear spin relaxation in solids

We investigate the properties of ten spectral densities relevant for nuclear spin relaxation studies in solids. This is preceded by a brief review of nuclear spin relaxation in solids which includes a discussion of the appropriate spin-dependent interactions and the various relaxation rates which can be measured. Also, the link between nuclear spin relaxation and dielectric relaxation is discussed. Where possible and/or appropriate each of the spectral densities is expressed as a continuous distribution of Bloembergen-Purcell-Pound (or Debye) spectral densities 2ξ /(1 + ξ² ω²) for nuclear Larmor angular frequency ω and correlation time ξ. The spectral densities are named after their originators or the shape of the distributions of correlation times or both and are (1) Bloembergen-Purcell-Pound or δ-function, (2) Havriliak-Negami, (3) Cole-Cole, (4) Davidson-Cole, (5) Fang, (6) Fuoss-Kirkwood, (7) Bryn Mawr, (8) Wagner or log-Gaussian, (9) log-Lorentzian, and (10) Fröhlich or energy box. The Havriliak-Negami spectral density is related to the Dissado-Hill theory for dielectric relaxation. The spectral densities are expressed in a way which makes them easy to compare with each other and with experimental data. Many plots of the distributions of correlation times and of the spectral densities vs. various correlation times characterizing the distributions are given.     

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.     

Fluorescence-lifetime-based tomography for turbid media

We derive a novel algorithm to recover the in vivo distributions of fluorophores based on an asymptotic life-time analysis of time-domain fluorescence measurements with turbid tissue. We experimentally demonstrate the advantage offered by this method in localizing fluorophores with distinct lifetimes. This algorithm has wide applicability for diagnostic fluorescence imaging in the presence of several-centimeter-thick biological tissue, since fluorescence lifetime is a sensitive indicator of local tissue environment and interactions at the molecular level.     

Influence of Substituent and Solvent on the Radiative Process of Singlet Excited States of Novel Cyclic Azacyanine Derivatives

The photophysical properties of novel cyclic azacyanine derivatives have been investigated in acetonitrile, N-butyronitrile, methanol, ethanol, DMF and water. Introduction of electron donating or accepting groups on the cyclic azacyanine has a direct impact on the spectroscopic and photophysical properties. Irrespective of the nature of the substitution, azacyanine shows a general solvent relaxation in accordance with Lippert-Mataga’s prediction; however, in protic solvent, specific interactions are encountered. Fluorescence lifetime decay suggests a relaxation in the nanosecond time scale with monoexponential decay in polar solvents and biexponential decay in non polar solvents. The fluorescence lifetime of azacyanines are found to be longer than popular cy3 dyes. An electron donating substituent increases the fluorescence lifetime and influences the radiative process, whereas an electron withdrawing group marginally increases the excited state lifetime but remarkably enhances the radiative process. The fluorescence quantum yield of substituted cyclic azacyanine in water is noted to be at least five fold higher than the popular cy3 dye.     

Recurrence plots of experimental data: To embed or not to embed?

A recurrence plot is a visualization tool for analyzing experimental data. These plots often reveal correlations in the data that are not easily detected in the original time series. Existing recurrence plot analysis techniques, which are primarily application oriented and completely quantitative, require that the time-series data first be embedded in a high-dimensional space, where the embedding dimension d(E) is dictated by the dimension d of the data set, with d(E)>/=2d+1. One such set of recurrence plot analysis tools, recurrence quantification analysis, is particularly useful in finding locations in the data where the underlying dynamics change. We have found that for certain low-dimensional systems the same results can be obtained with no embedding. (c) 1998 American Institute of Physics.     

Generalized moment expansion for nonadiabatic transition reaction

We discuss the generalized moments of the nonadiabatic transition reaction by using the stochastic Liouville equation for the study of outer-sphere electron transfer in polar solvents characterized by Debye dielectric relaxation. We obtain an approximate expression for the generalized moments which incorporates the width of the transition with arbitrary initial condition far from equilibrium. For low barriers, we derive an analytical expression for the rate corresponding to harmonic potential surfaces in the overdamped regime. For Fokker-Planck operators of Smoluchowski type, we introduce a new method to solve all of the generalized moments by using the eigenfunction expansion method.     

Investigation of microwave dielectric relaxation process in the antiferroelectric phase of NaNbO3 ceramics

This letter reports microwave dielectric measurements performed in the antiferroelectric phase of NaNbO₃ ceramics from 100 to 450 K. Remarkable dielectric relaxation was found within the antiferroelectric phase and in the vicinity of the ferroelectric-antiferroelectric phase transition. Such dielectric relaxation process was associated with relaxations of polar nanoregions with strong relaxor-like characteristic. In addition, the microwave dielectric measurements also revealed an unexpected and unusual anomaly in the relaxation strength, which was related to a disruption of the antiferroelectric order induced by a possible AFE-AFE phase transition.     

Conformational and dielectric analysis of hydrogen bonded polar binary mixtures of propan-1-ol with propionaldehyde

The dielectric behaviour of polar liquids such as propan-1-ol, propionaldehyde and their equimolar binary mixture in non-polar solvent benzene is studied in the microwave frequency range using the cavity perturbation technique at 6.218 GHz (J band), 9.880 GHz (X band), 16.331 GHz (P band) and 24.951 GHz (K band). Ab initio geometry optimization is performed in the 6-31G (d) basis set using the Gaussian 94W program for both pure and binary systems of propan-1-ol and propionaldehyde. Dipole moments of the binary mixtures are calculated from the dielectric data using Higasi's method and compared with the ab initio results. Conformational analysis of the formation of hydrogen bond between the propan-1-ol and propionaldehyde is supported by the FT-IR spectra. The average relaxation times are calculated from their respective Cole–Cole plots.     

Oxygen-vacancy-related dielectric relaxation and conduction mechanisms in Bi5TiNbWO15 ceramics

This paper reports that the intergrowth ceramics Bi5TiNbWO15 （BW-BTN） have been prepared with the conventional solid-state reaction method. The dielectric and conductivity properties of samples were studied by using the dielectric relaxation and AC impedance spectroscopy in detail. Two distinct relaxation mechanisms were detected both in the plots of dielectric loss （tanδ） and the imaginary part （Z″） versus frequency in the frequency range of 10 Hz-13 MHz. We attribute the higher frequency relaxation process to the hopping process of the oxygen vacancies inside the grains, while the other seems to be associated with the space charges bound at the grain boundary layers. The AC impedance spectroscopy indicates that the conductivities at 625 K for bulk and grain boundary are about 1.12 × 10^-2 S/m and 1.43 × 10^-3 S/m respectively. The accumulation of the space charges in the grain boundary layers induces a space charge potential of 0.52 eV.     

Correlation studies on dielectric and thermodynamic parameters in the binary mixtures of N-methyl aniline and alcohols

The dielectric and thermodynamic studies on polar binary mixtures of N- methyl aniline with alcohols — propan-1-ol and propan-2-ol have been carried out, at different temperatures and mole fractions. LF impedance analyzer, Microwave bench and Abbe’s refractometer are used respectively in radio, microwave (X-Band) and high frequency regions to determine the dielectric data. The experimental data is used to correlate the dielectric and thermodynamic parameters — static permittivity, high frequency permittivity, Kirkwood effective correlation factor, corrective Kirkwood correlation factor, excess permittivity, excess Helmholtz free energy, dipole moment, excessive dipole moment, relaxation time, excess inverse relaxation time and the excess thermodynamic parameters. These parameters are used to interpret the molecular interactions between the molecular species of the liquid mixtures.     

Simultaneous one-dimensional fluorescence lifetime measurements of OH and CO in premixed flames

A method for simultaneous measurements of fluorescence lifetimes of two species along a line is described. The experimental setup is based on picosecond laser pulses from two tunable optical parametric generator/optical parametric amplifier systems together with a streak camera. With an appropriate optical time delay between the two laser pulses, whose wavelengths are tuned to excite two different species, laser-induced fluorescence can be both detected temporally and spatially resolved by the streak camera. Hence, our method enables one-dimensional imaging of fluorescence lifetimes of two species in the same streak camera recording. The concept is demonstrated for fluorescence lifetime measurements of CO and OH in a laminar methane/air flame on a Bunsen-type burner. Measurements were taken in flames with four different equivalence ratios, namely ? = 0.9, 1.0, 1.15, and 1.25. The measured one-dimensional lifetime profiles generally agree well with lifetimes calculated from quenching cross sections found in the literature and quencher concentrations predicted by the GRI 3.0 mechanism. For OH, there is a systematic deviation of approximately 30 % between calculated and measured lifetimes. It is found that this is mainly due to the adiabatic assumption regarding the flame and uncertainty in H₂O quenching cross section. This emphasizes the strength of measuring the quenching rates rather than relying on models. The measurement concept might be useful for single-shot measurements of fluorescence lifetimes of several species pairs of vital importance in combustion processes, hence allowing fluorescence signals to be corrected for quenching and ultimately yield quantitative concentration profiles.     

Effect of an azo dye (DR1) on the dielectric parameters of a nematic liquid crystal system

 The dielectric parameters and relaxation properties of azo dye (DR1) doped E7 and pure E7 liquid crystal (LC) have been investigated in a wide frequency range of 10 k–10 MHz through the dielectric spectroscopy method at room temperature. Dielectric anisotropy (Δε) property of the LC changes from the positive type to negative type and dielectric anisotropy values decrease with doping of DR1. The relaxation frequency f_r of E7 and E7/DR1 LC was calculated by means of Cole–Cole plots. Influence of bias voltage on the dielectric parameters has also been investigated.     

Ac conductivity study of lithium and potassium diphosphate LiK3P2O7 using impedance spectroscopy

In this work, a LiK₃P₂O₇ ceramic material was prepared by the solid-state reaction method and identified by X-ray diffractometry. The dielectric properties, impedance characteristics, and modulus were studied over a range of frequency (200 Hz to 5 MHz) and temperature (615–708 K). The frequency and temperature dependence of dielectric permittivity, dielectric loss, and electric modulus is studied. The frequency analysis of modulus properties showed a distribution of relaxation times. Conductivity plots against frequency at a higher frequency suggested the response obeying the universal power law. The temperature behavior of the frequency exponents shows that the correlated barrier hopping CBH model is well adapted to this material. The activation energy associated with the impedance relaxation and the electric modulus spectra is close to the activation energy for dc conductivity indicating the similar nature of relaxation and conductivity. Thermodynamic parameters such as free energy of activation, enthalpy, and entropy have been calculated.     

Microwave dielectric absorption studies of hydrogen bonded polar binary mixtures of isobutanol with tertiary butyl amine

The dielectric behaviour of polar liquids like isobutanol, tertiary butyl amine and their equimolar binary mixture in nonpolar solvent benzene is studied in the microwave frequency range using the cavity perturbation technique at 6.218?GHz (J band), 9.880?GHz (X band), 16.331?GHz (P band) and 24.951?GHz (K band). Hamiltonian quantum mechanical calculations such as AM1, PM3 and MNDO optimized converged geometry operation is performed on isobutanol, tertiary butyl amine and their equimolar binary mixtures using Argus lab chemical modelling software, 2004. Dipole moments of the binary mixtures are calculated from the dielectric data using Higasi's method, and compared with the theoretical Hamiltonian quantum mechanical results. Conformational analysis of the formation of hydrogen bond between the isobutanol and tertiary butyl amine is supported by FT-IR and proton NMR spectra. The average relaxation times are calculated from their respective Cole–Cole plots.