Impedance spectra of polymer electrolytes

The authors present a phenomenological view on dielectric relaxation in polymer electrolytes. Polymer electrolytes are seen as molecular mixtures of an organic polymer and an inorganic salt. The following is based on systems with high molar mass poly(ethylene oxide) (PEO) and epoxidized natural rubber with 25 mol% of epoxide content (ENR-25) filled with lithium perchlorate (LiClO₄). Dielectric properties of these systems have been studied as a function of salt content at room temperature. Additionally, properties of neat low molar mass PEO were studied as function of temperature. Relaxation-coined dielectric behavior rules the system with PEO in the frequency that ranged up to 10⁶ Hz. Imaginary parts of impedance, tangent loss, and electric modulus spectra show distribution of relaxation times. Comparison of tangent loss (tan δ) spectra and imaginary part of electric modulus (M″) spectra reveals that localized motion dominates long-range motion of dipoles in the low-frequency range. However, discrepancy between them decreases with growing salt content. Scaling of tan δ spectra demonstrates that distribution of relaxation times does not depend on salt content in the range of low frequencies. The ENR-25 system exhibits solely relaxation like a macroscopic dipole. In conclusion, the system with PEO is characterized by individual relaxation of well-interacting dipoles, whereas the system based on ENR-25 is coined by immobilized dipoles that lead in the state of high-salt content to the relaxation behavior of a macroscopic dipole.     

New model of electron stimulated desorption from physisorbed monolayers application to Ar and N2O on Ru(001)

A new model of electron stimulated desorption from monolayers physisorbed on metal surfaces is proposed in which the excited surface state potential is due to a chemical rather than an image force acting on the adsorbed particle after the initial electronic excitation is completed. The equilibrium positions of the excited and the ground state potentials may nearly coincide and desorption is a purely quantum mechanical effect. It is demonstrated that, unlike for the commonly accepted Antoniewicz model, both, the kinetic energy distributions of desorbing neutral particles and the total desorption yields calculated in the model proposed here are consistent with the existing experimental data for Ar and N₂O physisorbed on Ru(001).     

Temporal dependence of the dipole moment of long-wavelength forms of n-dimethylaminobenzonitrile

The temporal dependences μ_e(t) of the dipole moment of n-dimethylaminobenzonitrile excited to different states by quanta with different energies are evaluated based on the experimental correlation functions of the shift of instantaneous spectra. It is found that, upon excitation into the maximum of absorption, the relaxation changes of the spectra are accompanied by an increase in the dipole moment from 9 D in the Franck-Condon state to 16 D in the stationary state. At the same time, the excitation of luminescence at the red absorption edge by radiation at 403 nm leads to a decrease in the range of variation of the dipole moment. In this case, the initial value of the dipole moment amounts to 14 D and, during the lifetime of the excited state, it increases to 17 D. This indicates that the nature of the radiation excited at the wavelength 403 nm is directly related to internal charge transfer states of n-dimethylaminobenzonitrile.     

Dielectric relaxation of CdSe nanoparticles

Nanoparticles of cadmium selenide (CdSe) have been synthesized by soft chemical route using mercaptoethanol as a capping agent. X-ray diffraction and transmission electron microscope measurements show that the prepared sample belongs to sphalerite structure with the average particle size of 25 nm. The band gap of the material is found to be 2.1 eV. The photoluminescence (PL) emission spectra of the sample are measured at various excitation wavelengths. The PL spectra appear in the visible region, and the emission feature depends on the wavelength of the excitation. Impedance spectroscopy is applied to investigate the dielectric relaxation of the sample in a temperature range from 323 to 473 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). The dielectric relaxation of the sample is investigated in the electric modulus formalism. The temperature dependent relaxation times obey the Arrhenius law. The Havriliak–Negami model is used to investigate the dielectric relaxation mechanism in the sample. The frequency dependent conductivity spectra are found to obey the power law.     

Retardation of the relaxation over quantum-well energy levels in CdSe/ZnS quantum dots with increasing number of excited carriers

The differential transmission spectra of CdSe/ZnS quantum dots are investigated. It is revealed that the differential transmission spectra measured upon resonant excitation of electrons into the first excited state 1P(e) exhibit a number of specific features, such as a decrease in transmission at the pump frequency, bleaching in the course of the pump pulse at frequencies corresponding to the fundamental optical transition 1S _3/2(h)-1S(e) and transitions between excited hole states and the 1S(e) electron ground state, and retardation of this process with an increase in the energy of the pump pulse. The observed specific features can be explained by the following factors: (i) the absence of a “phonon bottleneck” for electrons due to the energy transfer from hot electrons to rapidly relaxing holes, (ii) relaxation through intermediate quantum-well energy levels of holes, and (iii) retardation of relaxation with increasing number of excited charge carriers in a quantum dot.     

An impedance spectroscopy study in poly(butylene adipate) ionomers

Poly(butylenes adipate) ionomers (PBAi) were synthesized using dimethyl 5‐sulfoisophthalate sodium salt (DMSI) up to 5 mol% of diacid monomer. We have investigated electrical and dielectric properties of the ionomers to evaluate alternating current (AC) parameters such as impedance, conductance, dielectric constant, admittance, susceptance, dielectric loss, and resistance by an impedance spectroscopy. It is seen that the ionic conductances of the ionomers increase with increasing content of DMSI. The AC conductance for the ionomers was found to vary as ω^s with the index s ≥ 1. A decrease in the relative dielectric constant of the ionomers is observed with the increase in the ionic content. The electrical relaxation in the dielectric spectra of the ionomers was not observed due to the orientation polarization of the dipoles. It is also observed that the tangent loss increases with the increase in the ionic content.     

Ultrafast S1 and ICT state dynamics of a marine carotenoid probed by femtosecond one- and two-photon pump-probe spectroscopy

Ultrafast relaxation kinetics of fucoxanthin in polar and non-polar solvents have been studied by femtosecond pump-probe spectroscopy. Transient absorption associated with S₁ or intramolecular charge transfer (ICT) excited state has been observed following either one-photon excitation to the optically allowed S₂ state or two-photon excitation to the symmetry-forbidden S₁ state. The results suggest that the ICT state formed after excitation of fucoxanthin in a polar solvent is a distinct excited state from S₁.     

Influence of electron-atom cross section uncertainties on shock wave structure

The exact value of the electron-atom collisional ionization cross section for argon is not accurately known. The purpose of the present research is to determine numerically the effect of varying the magnitude of the electron-atom cross section on nonequilibrium shock-wave structure. Mach 18 shock waves propagating into an argon-like gas at 1 cm-Hg and 300°K have been analyzed. Thermal, ionizational, and excitational non-equilibrium are considered in the relaxation region behind the shock wave. Electrons in the relaxation region are formed by a two-step collisional process, wherein the atom is first excited and then it is ionized. The precursor is formed by ground and excited state continuum radiation and line radiation which is emitted, but not reabsorbed, in the region behind the shock wave. When the electron-atom ionization cross section is varied from 1·86 × 10^?4to 1·86 × 10^?2cm²/erg, the results show that (1) it influences the coupling between the precursor and relaxation region through the radiative source functions, (2) it does not influence the distance necessary to attain equilibrium behind the shock wave, (3) it inversely influences the magnitude of the precursor ionization, and excitation, and (4) it inversely influences both the free electron and excited state population in the relaxation layer.     

Microscopic theory of brownian motion: III. The nonlinear Fokker-Planck equation

The nonlinear Fokker-Planck equation for the momentum distribution of a brownian particle of mass M in a bath of particles of mass m is derived. The contribution to this equation arising from initial deviation from bath equilibrium is analysed. This contribution is free of slow M-dependent decays and with certain restrictions leads to an effective shift in the initial value of the B particle momentum. The nonlinear Fokker-Planck equation for an initial bath equilibrium state is analyzed in terms of its predictions for momentum relaxation and mode coupling effects. It is found that in addition to nonlinear renormalization of the type previously found for the momentum correlation function, mode coupling leads to long-lived memory of the initial momentum state.     

Influence of the polarity of a medium on the photonics of a merocyanine dye with a high quadratic polarizability

The influence of the polarity of a medium on the spectral and luminescent properties of 2-[(2E,4E)-6-(1,3,3-trimethyl-2,3-dihydro-1H-2-indolyliden)-2,4-hexadienyliden]malononitrile (THDM) in solutions and polymer matrices is studied at room temperature under conditions of steady-state and pulsed laser excitation. A large bathochromic shift of the absorption spectra observed upon an increase in the polarity of a solvent is caused by a strong increase in the molecular dipole moment μ due to a transition of molecules from the ground state (μ_g = 7.6 D) to an excited Franck-Condon state (μ^FC = 33.5 D). Based on the solvatochromic data, the quadratic polarizability was calculated to be β = (3.2 ± 0.6) × 10^?28 esu, which is close to the experimentally determined value β_ex = (3.9 ± 0.2) × 10^?28 esu. A strong narrowing of the fluorescence spectra in comparison with the absorption spectra is observed upon an increase in the solvent polarity. This narrowing is explained by a decrease in the bond length alternation parameter and by weakening of vibronic interactions in the singlet excited state. The dynamic solvatofluorochromism of THDM in the picosecond range is caused by reorientations of molecules of the polar environment occurring during a time period consistent with the dielectric relaxation time of these molecules.     

Effect of B-site isovalent doping on electrical and ferroelectric properties of lead free bismuth titanate ceramics

In the present work, zirconium modified bismuth titanate ceramics have been studied as potential lead-free ferroelectric materials over a broad temperature range (RT – 800 °C). Polycrystalline samples of Bi₄Ti_3−xZr_xO₁₂ (x=0.2, 0.4, 0.6) (BZrT) with high electrical resistivity were prepared using the solution combustion technique. The effect of Zr doping on the crystalline structure, ferroelectric properties and electrical conduction characteristics of BZrT ceramics were explored. Addition of zirconium to bismuth titanate enhances its dielectric constant and reduces the loss factor as it introduces orthorhombic distortion in bismuth titanate lattice which is exhibited by the growth along (0010) lattice plane. Activation energy due to relaxation is found to be greater than that due to conduction thus confirming that electrical conduction in these ceramics is not due to relaxation of dipoles. Remanent polarization of the doped samples increases as the Zirconium content increases.     

Plasma response to transient high voltage pulses

This review reports on plasma response to transient high voltage pulses in a low pressure unmagnetized plasma. Mainly, the experiments are reviewed, when a disc electrode (metallic and dielectric) is biased pulsed negative or positive. The main aim is to review the electron loss in plasmas and particle balance during the negative pulse electrode biasing, when the applied pulse width is less than the ion plasma period. Though the applied pulse width is less than the ion plasma period, ion rarefaction waves are excited. The solitary electron holes are reviewed for positive pulsed bias to the electrode. Also the excitation of waves (solitary electron and ion holes) is reviewed for a metallic electrode covered by a dielectric material. The wave excitation during and after the pulse withdrawal, excitation and propagation characteristics of various electrostatic plasma waves are reviewed here.     

Investigation on crystalline structure and dielectric relaxation behaviors of hot pressed poly(vinylidene fluoride) film

The dielectric relaxation behaviors of hot pressed poly(vinylidene fluoride) (PVDF) film have been studied using dielectric spectroscopy in the frequency domain from 20 Hz to 5 MHz at temperatures between 20 °C and 200 °C. Crystalline/amorphous interphase is suggested with methods of FTIR, XRD, and DSC. Frequency and temperature dependence of dielectric spectroscopy reveals the relaxation behavior and structural dynamics of the samples, and three types of relaxation processes are suggested, α_Ac relaxation process contributed by the hopping transport process near the periphery of conduction band or valence zones at Fermi energy, α_c relaxation process related to the structure change of crystal lattice trapped dipoles in crystalline regions, and α_a relaxation process arising from segmental dipole rearrangement of interphases in amorphous regions. Cole-Cole and Havriliak-Negami experimental equations were utilized to analyze these relaxation processes, and differences of Arrhenius parameters for α_Ac and α_c relaxation processes obtained from Cole-Cole and Havriliak-Negami equations were discussed in detail. Activity energy of different relaxation processes obtained from Arrhenius equation and VFT equation indicates non-single thermal activation mechanism for hot pressed PVDF film.     

Light-induced ultrafast phase transitions in VO2 thin film

Vanadium dioxide shows a passive and reversible change from a monoclinic insulator phase to a metallic tetragonal rutile structure when the sample temperature is close to and over 68 °C. As a kind of functional material, VO₂ thin films deposited on fused quartz substrates were successfully prepared by the pulsed laser deposition (PLD) technique. With laser illumination at 400 nm on the obtained films, the phase transition (PT) occurred. The observed light-induced PT was as fast as the laser pulse duration of 100 fs. Using a femtosecond laser system, the relaxation processes in VO₂ were studied by optical pump-probe spectroscopy. Upon a laser excitation an instantaneous response in the transient reflectivity and transmission was observed followed by a relatively longer relaxation process. The alteration is dependent on pump power. The change in reflectance reached a maximum value at a pump pulse energy between 7 and 14 mJ/cm². The observed PT is associated with the optical interband transition in VO₂ thin film. It suggests that with a pump laser illuminating on the film, excitation from the d_θ,? - state of valence band to the unoccupied excited mixed d_θ,?-π* - state of the conduction band in the insulator phase occurs, followed by a resonant transition to an unoccupied excited mixed d_θ,?-π* - state of the metallic phase band.     

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.     

Two-laser two-color time-resolved EPR study on higher-excited-state triplet-singlet intersystem crossing of porphyrins and phthalocyanines

Photoinduced effects on the electron spin polarization (ESP) in the lowest excited triplet (T₁) states of porphyrins (PORs) and phthalocyanines (PCs) have been observed with a two-color time-resolved (TR) electron paramagnetic resonance (EPR) technique in a glassy matrix at low temperatures. On single-color excitation with the wavelengths of the ground state absorptions of PORs and PCs, polarized EPR spectra due to the corresponding T₁ state were observed. The polarization patterns match well with interpretation as anisotropic intersystem crossing (ISC) induced by the spinorbit coupling between the singlet excited (S₁) and the triplet states. In contrast, two-color excitation led to a change of the phase of the T₁ state polarization pattern to the opposite. The observed ESP in the T₁ state resulting from the excitation to the upper triplet state (T _n ) was interpreted in terms of anisotropic ISC between the T _n and S₁ states. From the analysis of the ESP, changes in the quantum yields of the reverse ISC processes were determined at different temperatures. The results could be best interpreted by the existence of thermal pathways with small activation energy in the relaxation processes.     

A statistical approach to describe highly excited heavy and superheavy nuclei

A statistical approach based on the Weisskopf evaporation theory has been developed to describe the deexcitation process of highly excited heavy and superheavy nuclei, in particular for the proton-rich nuclei. The excited nucleus is cooled by evaporating γ-rays, light particles(neutrons, protons, α etc) in competition with binary fission,in which the structure effects(shell correction, fission barrier, particle separation energy) contribute to the processes.The formation of residual nuclei is evaluated via sequential emission of possible particles above the separation energies.The available data of fusion-evaporation excitation functions in the ~(28)Si+~(198)Pt reaction can be reproduced nicely within the approach.     

Origin of dielectric relaxations in KHSeO4 above room temperature

The dispersion curves of the dielectric response for KHSeO₄ were obtained in the radio frequency range at several isotherms below the fast proton conducting phase (T?<?415 K). The results reveal a distinct dielectric relaxation at low frequency, which is about 682 Hz at 320 K, and then, it shifts to higher frequencies (～10 kHz) as the temperature increases. The f _max vs. reciprocal T shows an activated relaxation process with an activation energy of 0.5 eV, which is in close agreement with that associated with transport of charge carriers. We suggest that the observed dielectric relaxation could be attributed to polarization induced by the proton jump and selenate tetrahedral reorientations. The displacement of mobile H⁺ proton accompanied by SeO ₄ ^??2 tetrahedra reorientations creates structural distortion in both sublattices which induce localized dipoles like HSeO ₄ ^? .     

Excitation-wavelength Dependent Fluorescence of Ethyl 5-(4-aminophenyl)-3-amino-2,4-dicyanobenzoate

The excitation wavelength dependence of the steady-state and time-resolved emission spectra of ethyl 5-(4-aminophenyl)-3-amino-2,4-dicyanobenzoate (EAADCy) in tetrahydrofuran (THF) at room temperature has been examined. It is found that the ratio of the fluorescence intensity of the long-wavelength and short-wavelength fluorescence bands strongly depends on the excitation wavelength, whereas the wavelengths of the fluorescence excitation and fluorescence bands maxima are independent on the observation/excitation wavelengths. The dynamic Stokes shift of fluorophore in locally excited (LE) and intramolecular charge transfer (ICT) states has been studied with a time resolution about 30 ps. The difference between Stokes shift in the LE and ICT states was attributed to the solvent response to the large photoinduced dipole moment of EAADCy in the fluorescent charge transfer state. On this base we can state that, the relaxation of the polar solvent molecules around the fluorophore was observed.     

Molecular nanocluster fluorescence in microwave infrared-radiation fields

The paper considers a donor-acceptor nanocluster fluorescing in a microwave infrared radiation field. It is assumed that the nanocluster consists of two dipole-dipole interacting organic molecules. It is shown that the fluorescence process of the nanocluster occurs if the donor molecule contains a substructure of identical diatomic pairwise interacting bonds of dipoles (an IR antenna). This antenna is capable of accumulating vibrational energy as a sum of collective vibrational quanta (excimols). The acceptor molecule has no permanent dipole moment and cannot be excited by microwave IR radiation. This molecule is polarized in the dipole moment field of the donor IR antenna and can receive energy accumulated in the IR antenna of the donor molecule. If the acceptor molecule has an electronically excited state in the long-wavelength visible region of its absorption spectrum, then after receiving energy equal to the energy of this state from the donor antenna, the electronic excitation of the acceptor molecule and its fluorescence is possible. As an example, the fluorescence of a nanocluster is considered whose donor molecule has a C _n H_2n IR antenna. The acceptor molecule is aromatic and the external infrared frequency, 1.1 × 10¹⁴ s^?1, is equal to the frequency of the excimol in the donor infrared antenna.