Electronic structure and optical properties of lead chloride

Spectra for the sets of optical functions for lead chloride are obtained for polarizations E ‖ a and E ‖ b at 10 K in the range of 4 to 30 eV. The calculations are carried out using synchrotron reflectivity spectra and a software package. The main features of the spectra of optical functions were established; they include the energies for volume and surface plasmons of two types. The bands and the spectra of permittivity and other optical functions for lead chloride crystals are calculated using the FP LAPW method. There was good agreement between the theoretical calculations and the data of the experimental spectra of R and other optical functions calculated using these R spectra.     

Spatial dispersion in polariton spectra of CuGaS2 crystals

The unmodulated and wavelength-modulated reflectivity spectra of CuGaS₂ crystals for the polarization E ‖ c, k ⊥ c at 77 and 8 K have been studied. The states n=1, 2, and 3 of A excitons and n=1 and 2 of B and C excitons are established. The luminescence spectra from the surface at k ‖ c and k ⊥ c are obtained. The fine structure of the reflectivity spectra of excitons are analyzed with due regard for the normal and oblique incidence of light onto the crystal surface. The main parameters of the A, B, and C excitonic series are determined such as the energies of the longitudinal and transverse excitons Γ₄ (E ‖ c) for states n=1 and 2, the longitudinal and the transverse mass of excitons in CuGaS 2, and the effective masses of electrons (m _c1*) and holes (m _v1*, m _v2*, m _v3*). It is shown that the mass m _v1* in the upper valence band at k ‖ c equals (0.7–0.8)m ₀ and at k ⊥ c, 1.87m ₀.     

Optical Constants of an Apatite Single Crystal in the IR Range of 6–28 μm

On the basis of polarized IR-reflection spectra in the range of 5000–350 cm^–1 measured from the natural face of an optically transparent fluorapatite single crystal, components of a complex refractive index (optical constants) for radiation-vector orientations E ‖ c and E ⊥ c have been calculated by the Kramers–Kronig method. The fluorapatite single crystal has been chosen from several samples: it contains a minimum amount of impurities and has a high degree of crystallinity in accordance with the criteria of IR spectroscopy and Raman spectroscopy. Tabular data on optical constants for ordinary and extraordinary rays are given for the IR range of 6–28 μm. The obtained absorption spectra are compared with the results of quantum-chemical ab initio calculations within the B3LYP simulation.     

Aging effect in CaLaBa{Cu1???xFex}3O7???�� with 0 �� x �� 0.07 studied by M?ssbauer spectroscopy

In this work, we study the long-term aging effect caused by Fe atoms in the superconductor CaLaBa{Cu_1???xFe_x}₃O_7????? with 0 ?? x ?? 0.07. XRD confirms that this system has a YBCO-like structure. The critical temperature (T_c) is strongly affected by aging and depends on the amount of Fe in the structure. Room temperature Mössbauer spectroscopy reveals the presence of the typical species A, B?CB ??, C and new species E ?? and F. Interestingly; A, which corresponds to the Fe^3?+? atom located in the Cu(1) of the chains with spin S _z = 3/2, shows a drastic reduction which means migration to the species B, B ?? and C. Species B and B ?? correspond to the Fe^3?+? in the Cu(2) site forming planar quasi-octahedral and planar square pyramidal, while the C specie is a square pyramidal with O(5) respectively (spin S_z = 3/2 in all these cases). Aging causes loss of superconductivity in the samples with 5 and 7% of iron content.     

The Optical Spectra of the Arsenic Triselenide Crystal in the Range from 1 to 10 eV

Full complexes of fundamental optical functions of the As₂Se₃ single crystal in the region from 1 to 10 eV are calculated at 10 K (1–5.5 eV) and 77 K (5.5–10 eV) for three light polarizations (E a, E b, and E c). Their main characteristic features are established. The experimental reflection spectra and the spectra of other optical functions calculated on their basis are compared with the known literature data.     

A Novel Series Colorimetric and Off–On Fluorescent Chemosensors for Fe3+ Based on Rhodamine B Derivative

A novel series colorimetric and off–on fluorescent chemosensors (2a, 2b, 2c) were designed and synthesized, which showed reversible and highly selective and sensitive recognition toward Fe³⁺ over other examined metal ions. Upon addition of Fe³⁺, sensors (2a, 2b) exhibit remarkably and 2c exhibits moderate enhanced absorbance intensity and color change from colorless to pink in CH₃OH–H₂O(1:1, v/v). The three compounds (2a, 2b, 2c) may therefore be applicable as rhodamine-based turn-on type fluorescent chemosensors.     

Structurally Simple Ferrocene Derivatives for Selective Cadmium Sensing

Three new ferrocene based Schiff bases 4-{[(E)-ferrocenylmethylidene] amino}benzenethiol (1b), 3-{[(E)-ferrocenylmethylidene]amino} benzenethiol (1c), 2-{[(E)-ferrocenylmethylidene]amino} benzenethiol (1d) have been synthesized to study their sensor property to various metal ions. It has been observed that 1b is highly fluorescent and its fluorescence changes in presence of metal ions. It was further observed that compound 1b is highly selective towards Cd²⁺ ion in solution.     

Edge absorption spectra of crystalline and glassy PbGeS<Subscript>3</Subscript>

Edge absorption spectra of crystalline and glassy lead thiogermanate (PbGeS₃) have been measured in the temperature range from 77 to 470 K. It is shown that the dependence of the absorption coefficient on the photon energy for the glassy and crystalline states in the polarization E ∥ c is described by the Urbach rule. For the crystal in the polarization E ∥ b, at T < 300 K, an almost parallel shift of the intrinsic absorption edge to lower energies occurs with an increase in temperature, whereas at T ≥ 300 K, the Urbach absorption edge is observed. The parameter σ₀, related to the electron-phonon coupling constant, and the energy ?ω_ph of the effective phonons involved in the formation of the absorption edge of crystalline PbGeS₃ are determined from the temperature dependence of the parameter of the absorption edge slope. The contributions of the dynamic and static disorders to the diffusion of the absorption edge of crystalline PbGeS₃, as well as the topological disorder of glassy PbGeS₃, have been estimated.     

Trovacenyl-based organometallic triradicals: Spin frustration, competing interactions and redox splitting

Two new triradicals based on trovacene [η⁷-tropylium)vanadium(η⁵-cyclopentadienyl)], 1,3,5-tri([5]trovacenyl) benzene4 and 1,3,5-tri([5]trovacenyl)-6-methoxybenzene5 were prepared and their magnetic properties were studied by continuous-wave X-band electron paramagnetic resonance (EPR) spectroscopy and by temperature-dependent magnetic susceptometry. The EPR spectra of4 and5 in liquid toluene solution demonstrate that the three unpaired electrons localized on the vanadium atoms interact with each other in both complexes. The data from magnetic susceptometry revealed that the electron spins in both triradicals are antiferromagnetically coupled despite themeta-phenylene bridge. The exchange coupling constants are equal in the C₃-symmetrical triradical4 (J=J′=?0.68 cm^?1), which leads to a twofold degenerate spin ground state (spin frustration). The symmetry lowering by methoxy substitution of the benzene spacer in5 results in the effect of c ompeting interactions (J=?1.83 cm^?1 andJ′=?2.38 cm^?1). In addition to magnetocommunication, the effect of ring substitution on electrocommunication is also discernable. It manifests itself indisparate redox splittings δE _1/2 (0/?, ?/2?) and δE _1/2 (?/2?, 2?/3?) for5, while these parameters are equal for the C₃-symmetrical trinuclear complex4.     

Magnetostriction and thermal expansion of HoAl3(BO3)4

The magnetostriction and thermal expansion of rare-earth aluminoborate HoAl₃(BO₃)₄ have been studied theoretically. The calculated field and temperature dependences of the multipole moments of the Ho³⁺ ion in HoAl₃(BO₃)₄ made it possible to describe the known experimental data and to predict possible anomalies of thermal expansion. It has been shown that, for the direction of the field B ‖ c, the nonmonotonic character of magnetostriction along the axis a is determined by the multipole moments, the main of which is β _J 〈O ₄ ⁰ 〉. For B ‖ a and B ‖ b, the maximum moments are β _J 〈O ₄ ² 〉and α _J 〈O ₂ ² 〉; their variation with the field and temperature explain well the form of magnetostriction. It has been established that the greater value of magnetostriction Δa/a for B ‖ b than for B ‖ a and the greater value of magnetostriction for the field in the basal plane than for B ‖ c are caused by greater variations in the field of actual multipole moments.     

Anisotropic resonant magnetoplasticity of NaCl crystals in the Earth’s magnetic field

Resonant relaxation of the dislocation structure under the action of crossed magnetic fields, i.e., constant magnetic field of the Earth (B _Earth) and alternating radio-frequency field ( $\tilde B$ ), has been experimentally studied in a series of dielectric (NaCl) crystals with various compositions of impurities under variations in the frequency, direction of the pumping field $\tilde B$ , and orientation of the samples in the Earth’s magnetic field. The frequency dependence of the dislocation path length l(ν) exhibits peaks with various heights (l _max) and resonant frequencies (ν_res). The maximum resonant effect has been observed for dislocations with the direction L orthogonal to the plane of crossed magnetic fields in a configuration of mutually perpendicular vectors {L, $\tilde B$ , B _Earth} belonging, together with sample edges {a, b, c}, to the 〈100〉 system. Variation of the concentration C of calcium impurity in crystals of the NaCl_Ca series only influenced the resonant peak height as $l_{\max } \propto 1/\sqrt C $ . Rotation of the magnetic field $\tilde B$ in the (b, c) plane from direction $\tilde B$ ⊥ B _Earth to $\tilde B$ ∥ B _Earth also did not influence the frequency of the resonance but changed its amplitude. Depending on the crystal type, this influence changed from rather insignificant (in crystals of the NaCl_LOMO series) to complete suppression of the effect for $\tilde B$ ∥ B _Earth (in the NaCl_Nik series). The resonant frequency ν_res is sensitive to orientation of the sample with respect to B _Earth. Upon rotation of the crystal by the angle θ = ∠(c, B _Earth) about the a ⊥ B _Earth edge, the initial peak for dislocations L ‖ a at the crystal orientation θ = 0 and the frequency ν _res ⁰ is replaced by a pair of peaks at frequencies ν_{1, 2} ≈ ν _res ⁰ cosθ_{1, 2}, where θ₁ = 90° ? θ and θ₂ = θ. Previously, these peaks were observed separately in NaCl_Nik crystals for $\tilde B$ ∥ c and $\tilde B$ ∥ b. In the present study, these peaks have been observed simultaneously for both orientations of $\tilde B$ in NaCl_LOMO and NaCl_Ca crystals, where the resonance is not completely suppressed for $\tilde B$ ∥ B _Earth.     

Specific features of the thermal electromotive force in Bi quantum wires in transverse magnetic and electric fields

The thermal electromotive force (emf) in Bi quantum wires has been calculated in the model of potential in the form of a paraboloid of revolution in a uniform magnetic field H, which is normal to the axis of the studied nanostructure, and in a direct-current (dc) electric field E ‖ H. It has been shown that, with an increase in E, the thermal emf α _xx is described by a nonmonotonic function at different values of H. A physical interpretation of this behavior of α _xx as a function of E is proposed with account for the interaction between carriers and the rough surface of the nanowire.     

Laser fields at flat interfaces: II. Plasmon resonances in aluminium photoelectron spectra

Using the model derived in paper I?[G. Ra?eev, Eur. Phys. J. D 66, 167 (2012)], this work presents calculations of the photoelectron spectrum (PES) of low index aluminium surfaces in the 10?C30?eV region. The laser is p or transverse magnetic linearly polarized incident on a flat structureless surface and its fields are modeled in I using the vector potential in the temporal gauge. This model uses a tensor and non-local isotropic (TNLI) susceptibility and solves the classical Ampère-Maxwell equation through the use of the vector potential from the electron density-coupled integro-differential equations (VPED-CIDE). The PE cross sections are the squares of the PE transition moments calculated using the VPED-CIDE vector potential function of the penetration coordinate. The PES is obtained in a one step model using either the Fermi golden rule or the Weisskopf-Wigner (WW) expressions. The WW cross section PES compares favorably with the experimental angle and energy resolved photoelectron yield (AERPY) spectrum of Levinson et?al. [Phys. Rev. Lett. 43, 952 (1979)], Levinson and Plummer [Phys. Rev. B 24, 628 (1981)] for Al(001) and of Barman et?al.?[Phys. Rev. B 58, R4285 (1998)], Barman [Curr. Sci. 88, 54 (2005)] for Al(111) surfaces. As in the experiment, our theoretical AERPY displays the multipole surface plasmon resonance at 11.32/12.75 eV for Al(001)/Al(111), mainly due to the surface contribution |??? _f |p·A|?? _i ?|², the bulk plasmon minimum at 15 eV and the two single particle excitation resonances at about 16 and 22 eV. The nature of the plasmon resonances of the PES is analyzed using the reflectance, the electron density induced by the laser and Feibelman??s parameter d _?? all introduced in paper?I.     

Stimulated multiphoton emission from exciton Bose condensate

The coherent recombination of several (N) Bose-condensed excitons with simultaneous creation of N photons is considered. Due to the momentum conservation law, the total momentum of created photons is zero because of the zero momentum of excitons in Bose condensate. This requirement, in conjunction with the fact that the photon wavenumbers are fixed and equal to approximately E _g /c (E _g is the semiconductor gap and c is the speed of light), determines the mutual orientation of the wavevectors of emitted photons. This can be seen from the photon angular correlation in the experiments with several appropriately oriented detectors operating in the time-coincidence mode. It is shown that, if these processes are induced by N? 1 external laser beams (each with wavevector k _i ), then a unidirectional radiation with recoil wavevector k=?∑_i k _i should emerge from the exciton system. The intensities of coherent three-and four-exciton recombination are estimated for the exciton system in Cu₂O.     

Photoinduced transformations in a thin-film waveguide AgCl-Ag composition under a green (532 nm) laser beam

A linearly polarized (E ₀) laser beam (λ = 532 nm) causes photoinduced transformations in an AgCl-Ag composition consisting of a thin waveguide AgCl film on glass covered by a layer of Ag nanoparticles. Before the illumination the sample exhibits an absorption band due to localized plasmons in nanoparticles. The illumination excites plasmons and leads to scattering of waveguide TE₀ modes. The interference of modes with the incident light beam leads to the development of a periodic structure, the lines of which are formed by Ag particles and directed along E ₀. The measured structure period coincides with the result of calculation based on solving the dispersion equation for the TE₀-mode. Measurement of absorption in the E ‖ E ₀ polarization reveals dichroism and a spectral hole (at λ ≈ nm). It is shown that the structures formed remain on the substrate after removing AgCl in a fixing agent. The dichroism value and dispersion change after fixing. The character of dichroism prior to fixing is recovered after depositing an AgCl layer (with the parameters retained) on the fixed film.     

Some estimates for magnetic fluctuations in a turbulent medium

A new integral relationship between the fluctuations b(r, t) of a magnetic field and its mean B ₀(r, t) is derived for the steady-state magnetic field in a turbulent medium. This formula provides the estimate 〈b?curlb〉=?B ₀?curlB ₀. Simultaneously, the coefficient of amplification of the mean magnetic field α effect) is obtained: α=(η+β)B ₀? curlB ₀/B ₀ ² . The formula for α allows for a decrease in this coefficient owing to the back action of the magnetic field on the turbulent velocity field. It is shown that the Zel’dovich’s estimate 〈 b ²〉?β/η B ₀ ² for two-dimensional turbulence holds for magnetic fields at the instant the fluctuations 〈a ²〉 of the vector potential, rather than 〈b ²〉, reach a maximum. Here, η and β are the ohmic (molecular) and turbulent diffusion coefficients, respectively. This estimate is refined with allowance made for the fact that the condition for diffusion approximation itself relates the β, b, and B ₀ quantities to each other.     

The microwave absorption of high-T c superconducting thin film samples

The experimental and theoretical investigations of microwave losses (ML) in HTSC thin films are carried out. It is shown theoretically that ML in the maximum of the magnetic componentB ₁ are essentially larger than those in the maximum of the electric componentE ₁. This is because eddy currents make much more substantial contribution to ML as compared to conventional conductivity currents. The consequence of this is the angular dependence of ML with respect to theB ₁ field direction which was experimentally observed. The angular dependences of ML with respect to theB ₀ field direction for both low and highB ₀ values were also investigated. The majority of experimental data can be well explained within the mixed model which predicts the existence of a critical state in inter- and intragranular Josephson medium.     

Theory of spatial dispersion of dielectric and magnetic constants in magnetic uniaxial gyrotropic crystals

The theory of spatial dispersion of dielectric and magnetic constants of magnetic uniaxial crystals based on generalized Maxwell’s equations D = ε?E = (ε + inγ E = ?ns ^× H and B = μ?H = (μ + inδ)H = ns ^× E with spatial dispersion parameters γ and δ is considered. Generalized Fresnel’s and polarization equations for the obtained vectors E, D, H, and B are analyzed for the wave normal direction s ⊥ C (where C is the optic axis of a crystal). The possibility of the existence of a third natural wave in a crystal is proved.     

Dislocation structure of intermetallic Ti3Al subjected to high-temperature deformation

Transmission electron microscopy was used to examine the dislocation structure of intermetallic Ti₃Al subjected to deformation at tempertures T = 1073–1273 K. The microstructure of samples subjected to high-temperature deformation is established to contain mobile superdislocations of a and 2c + a types, and single dislocations with Burgers vector [0001] are also observed on the prismatic planes. Possible models of destruction of barriers associated with 2c + a superdislocations on the pyramidal planes are discussed using the results of computer simulations of the structure of a superdislocation core in in Ti₃Al.     

Magnetic properties of HoFe3(BO3)4

The magnetic properties of an antiferromagnet with trigonal symmetry, namely, HoFe₃(BO₃)₄, have been investigated theoretically. The calculations have been performed in the molecular field approximation and in the framework of the crystal field model for the rare-earth subsystem. Extensive experimental data on the magnetic properties of HoFe₃(BO₃)₄ have been interpreted and good agreement between theory and experiment has been achieved using the obtained theoretical dependences. The spontaneous spin-reorientation transition and the spin-reorientation transition induced by a magnetic field B ‖ a from the easy-axis to easy-plane state, as well as the spin-flop transition in a magnetic field B ‖ c, have been described. It has been shown that the spontaneous spin-reorientation transition is a magnetic analog of the Jahn-Teller effect. The temperature dependences of the initial magnetic susceptibility at temperatures ranging from 2 to 300 K, the nonlinear curves of magnetization for B ‖ c and B ⊥ c in a magnetic field up to 1.2 T (which indicate the occurrence of first-order phase transitions), and their evolution with variations in the temperature have been described, as well as the temperature and field dependences of the magnetization in a magnetic field up to 9 T. The parameters of the trigonal crystal field for the rare-earth ion Ho³⁺ and the parameters of the Fe-Fe and Ho-Fe exchange interactions have been determined in the course of interpretation of the experimental data.