Specific features of magnetic properties of “thick” microwires produced by the Ulitovsky-Taylor method

The magnetic properties of initial and heat-treated Co₆₉Fe₄Cr₄Si₁₂B₁₁ microwires in a glass shell with the diameter D = 125 μm and the diameter of the amorphous metallic core d = 90 μm produced by the Ulitovsky-Taylor method have been studied. It has been found that the magnetic characteristics, in particular, the saturation field H _S and the coercive force H _C of the samples annealed at a temperature T < 300°C do not differ from H _S and H _C of the initial microwire, and those of the samples annealed at T ≥ 400°C increase by almost one order of magnitude. The obtained experimental data have been explained by the structural features of the microwires. The near-surface values of H _S and H _C at T < 300°C are found to be larger than the bulk values by a factor of 5–10. These experimental data have been explained by the existence of structural and chemical ingomogeneities in the near-surface layer, which are inherent in amorphous materials. This difference decreases with a further increase in the annealing temperature, but H _S and H _C increase substantially. This fact has been explained by the beginning of the microwire crystallization.     

On electrostatic models of a metal-insulator phase transition in crystalline semiconductors with hydrogen-like impurities

Two well-known models for calculating the critical density N _C of a metal-insulator transition, as a function of the Bohr radius a _H of an isolated impurity as temperature T→0 K, are refined by making allowance for the screening of ions by electrons hopping along impurities. In one model, the transition at N _C1 is explained by the appearance of delocalized electrons as the impurity band is displaced into the allowed-energy band as a result of a decrease in the electron (hole) affinity of ionized impurities. In the other model the transition is explained by an unbounded increase in the static permittivity of the crystal as the density of impurity atoms increases to N _C2. The obtained approximations N _C1 ^1/3 a _H≈0.24 and N _C2 ^1/3 a _H≈0.20 for the degree of compensation K=0.01 describe existing experimental data for 1<a _H<10 nm. Fiz. Tverd. Tela (St. Petersburg) 40, 147–151 (January 1998)     

Calculation of the electronic structure and spectra for bacteriochlorophyll analogs

Geometric structures and excited electronic states for free bases of bacteriochlorin (H₂BC) and tetraazabacteriochlorin (H₂TABC) as well as for their magnesium complexes (MgBC and MgTABC), analogs of bacteriopheophytin a (H₂BPhea) and bacteriochlorophyll a (MgBPhea), have been calculated by a DFT method and by an INDO/Sm method (the INDO/S method with parameterization modified by the authors), respectively. The factors responsible for the observed bathochromic shift of the long-wavelength Q _x (0–0) band of MgBPhea relative to H₂BPhea, \updelta E_Qx @ - 300  \textc\textm ^{- 1} {{\updelta }}{E_{{Q_x}}} \cong - 300\;{\text{c}}{{\text{m}}^{ - 1}} , have been clarified. Contributions of one- and two-electron interactions to the resulting shift of the Q _x (0–0) band have been analyzed in detail for the H₂BC/MgBC, H₂TABC/MgTABC, and porphine (H₂P)/Mg porphine (MgP) pairs. It is shown that the bathochromic shift under consideration for the tetrahydro derivatives is caused by a decrease of the orbital energy gap ε₁–ε₋₁ between the lowest unoccupied and highest occupied molecular orbitals. The variation of δ(ε₁–ε₋₁) is large and amounts to –1660 and –920 cm^–1 for the H₂BC/MgBC and H₂TABC/MgTABC pairs, respectively. The two-electron contributions, both into the energy of electronic configurations and due to the superposition of the configurations, produce a compensating hypsochromic effect such that the shifts \updelta E_Qx {{\updelta }}{E_{{Q_x}}} are –260 and –150 cm^–1 for the H₂BC/MgBC and H₂TABC/MgTABC pairs, respectively. It is also shown that the calculated electronic spectra for the considered molecules agree quantitatively with the experimental absorption spectra.     

Magnetic field dependence ofT c and temperature dependence ofH c2 in layered superconductors with open normal state Fermi surface

A theoretical framework for treating the effects of magnetic fieldH on the pairing theory of superconductivity is considered, where the field is taken in an arbitrary direction with respect to crystal axes. This is applicable to closed, as well as open normal state Fermi surface (FS), including simple layered metals. The orbital effects of the magnetic field are treated semiclassically while retaining the full anisotropic paramagnetic contribution. Explicit calculations are presented in the limits |H| → |H _c2(T)|,T ∼ 0 andT →T _c(|H|), |H| ∼ 0. Effects of weak nonmagnetic impurity scattering, without vertex corrections, have also been taken into account in a phenomenological way. The final results for the case of open FS and layered materials are found to differ considerably from those of the closed FS. For example, an important parameter,h(T=0)=|H_c2(0)|/[-Tδ|H _c2 T|δT]_T{s0} for the case of a FS open ink _z-direction with thek _z-bandwidth, 4t ₃, very small compared to the Fermi energy,E _F, is close to 0.5906, compared to 0.7273 for the closed FS, in the clean limit. Analytical results are given for the magnetic field dependence ofT _c and the temperature dependence of H _c2 for a model of layered superconductors with widely open FS. For a set of band structure parameters for YBa₂Cu₃O₇ used elsewhere, we find reasonable values for the upper critical fieldH _c2(0), the slope (dH _c2/dT)_{T c0}, anisotropic coherence lengths ζ_i(T=0),i=x, y, z, and (dT _c/d|H|)_{|H| → 0}.     

ESR millimeter-band spectroscopy of magnetic ordering in the low-dimensional magnet CuGeO3

Resonant absorption of microwaves in CuGeO₃ single crystals in a frequency band of 40 to 120 GHz, in magnetic field B⩽15 T, at temperatures ranging between 0.5 and 300 K, and in the configuration B∥a has been investigated. Several absorption lines (S ₀, S _a, and S _b) whose parameters strongly depend on temperature have been detected close to ESR. The temperature dependence of the total absorption in the main line S ₀ with the Landé g-factor g ₀=2.154 at temperatures above the spin-Peierls transition temperature is in good agreement with Bonner and Fisher’s theoretical prediction for a one-dimensional Heisenberg spin chain. In addition to the main resonance, a resonance of smaller amplitude, S _a, with the g-factor g _a=2.72 has been detected at temperatures ranging down to a characteristic temperature T≃1 K, below which the amplitude of this feature drops to zero. A radical restructuring of the magnetoabsorption spectrum occurs at the temperature of the spin-Peierls transition T _SP≈14 K. At T<12 K new features emerge in the spectrum, namely, a broad absorption line overlapping with the narrow lines S ₀ and S _a, and a line S _b with g _b=1.83, which is not detected at temperatures above T _SP. An analysis of amplitudes and total absorption of ESR lines as functions of temperature has shown that the temperature range below 1 K is anomalous, which may be caused by an additional ordering in the CuGeO₃ magnetic subsystem at low temperatures. Zh. éksp. Teor. Fiz. 112, 1727–1738 (November 1997)     

Electronic structure of linear chains of fullerenes

The band structure of linear chains of fullerene molecules is calculated as a function of the intermolecular π-electron overlap integral T, which increases under increasing external pressure. Chains consisting of neutral (C₆₀) and charged (C ₆₀ ⁻ ) molecules are studied. It is shown that there is a sharp transition from a metal (or narrow-gap semiconductor) to an insulator (with band gap ∼1 eV)with increasing T. The proposed model makes it possible to describe the formation of solid-carbon struc-tures, containing chains of covalently bound fullerene molecules, with different pressure-dependent semiconductor properties. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 8, 647–650 (25 April 1997)     

Fast photoprocesses in a symmetric indotricarbocyanine dye (HITC) in solutions

Spectral-kinetic and photochemical properties of HITC dye with iodide and perchlorate counterions have been studied in environments where the dye molecules exist in different ionic forms. In ethanol, the dye molecules exist as free ions; in dichlorobenzene, as contact ion pairs. Superfast transformation of non-stationary spectra in an HITC dye bleaching band is found. The observed effects are interpreted within the framework of concepts on “burning out” a notch in the contour of a non-uniformly widened vibronic band of S ₀ → S ₁-absorption. Qualitative differences in recorded absorption spectra from the dye excited electronic states for weakly and highly polar solvents are found. It is shown that the observed differences are caused by superfast charge transfer in the contact ion pairs that results in the formation of free radicals.     

Particular features of manifestation of energy migration toward impurity in nanoparticles of metal complexes

We measure the fluorescence quantum yields (q _fl) of complexes of Al, Sc, Y, In, Lu, and Gd with dibenzoylmethane in aqueous and isopropanol solutions at different concentration ratios of ions and dike-tone. We reveal that, for the examined solutions, qfl of complexes varies more than by two orders of magnitude under the influence of the heavy atom. It is found that a considerable decrease in q _fl and τ_fl of ligands of complexes of listed ions caused by the influence of heavy atoms weakly affects the intensity of sensitized fluorescence of Nile red and rhodamine 6G molecules introduced into nanoparticles from these complexes in aqueous solutions. The revealed result is explained by the comparability of the singlet exciton free path length and the dimension of nanoparticles under study. We show that a lower fluorescence intensity of heavy metal complexes makes it possible to decrease its contribution in the range of the cofluorescence maximum of rhodamine 6G and to monitor the occurrence of the dye in the aqueous solution down to the concentration of 0.05 nM. We show that, in nanoparticles from Eu complexes, further fluorescence quenching of dibenzoylmethane is observed, as well as the appearance of cofluorescence of rhodamine 6G, the intensity of which is comparable with its intensity in nanoparticles of other complexes. The appearance of this cofluorescence cannot be explained by the existence of S-S energy migration.     

Probing the field-induced variation of the chemical potential in Bi2Sr2CaCu2Oy via magneto-thermopower measurements

Approximating the shape of the magneto-thermoelectric power (TEP) ΔS(T,H) measured in Bi₂Sr₂CaCu₂O_y by an asymmetric linear triangle of the form ΔS(T,H)≃S _p (H)±B ^±(H)(T _c −T) with positive B ⁻(H) and B ⁺(H) defined below and above T _c , we observe that B ⁺(H) ≃2B ⁻(H). To account for this asymmetry, we explicitly introduce the field-dependent chemical potential μ(H) of holes into the Ginzburg-Landau theory and calculate both an average ΔS _av(T,H) and fluctuation contribution ΔS _fl(T,H) to the total magneto-TEP ΔS(T,H). As a result, we find a rather simple relationship between the field-induced variation of the chemical potential in this material and the above-mentioned magneto-TEP data around T _c , viz. Δ μ(H)∝S _p (H). Zh. éksp. Teor. Fiz. 116, 257–262 (July 1999) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor.     

Anomalous absorption of ultrasound in gadolinium in a magnetic field

The absorption coefficient α _k for longitudinal ultrasonic (15 MHz) waves propagating transverse to the direction of a magnetic field H is measured in single crystal gadolinium. It is found that in fields H⩽600 Oe, the peak in α _k is shifted toward lower temperatures, while the absolute magnitude of the absorption rises with increasing H. It is shown on the basis of dynamic scaling that the anomalous behavior of α _k in fields H⩽600 Oe can be explained by introducing a magnetic field analog of the Landau-Khalatnikov relaxation mechanism. Fiz. Tverd. Tela (St. Petersburg) 39, 339–340 (February 1997)     

Molecular structure of trimethyl[(3-indole)ethoxy]silane cooled in a supersonic jet

Conformations of He-jet-cooled trimethyl[(3-indole)ethoxy]silane (TIES) have been studied using a laser spectroscopy technique in combination with quantum-chemical computations. Six probable conformers of the molecule were computed, of which only two conformations were observed. Based on an analysis of fluorescence excitation spectra, fluorescence spectra, shapes of rotational band contours at the electronic S₀–S₁ transition of TIES, and theoretical computations, the above conformers were assigned to steric structures. Twisted structures have the lowest energy due to intramolecular hydrogen bonds C - H ?O < _C^Si C - H \cdots O <_C^{Si} between hydrogen atoms of methyl groups and an oxygen atom and C–H···π between H and the π-electron cloud of the indole ring.     

Polarized fluorescence of β-carotene and related polyenes

The spectral and polarization characteristics of trans-isomers ofβ-carotene, lycopene, retinal, and 1,6-diphenylhexatriene (DPH) in solutions have been investigated by the methods of polarized fluorescence and semiempirical calculations of AM1 and RM3. The high and constant values of the degree of polarization P ∼0.46, closely coinciding with the limiting value P₀=0.5, according to the S₂→S₀-fluorescence and S₂←S₀-fluorescence excitation spectra ofβ-carotene and lycopene in n-hexane at room temperature and also high and coinciding according to the S₁→S₀-fluorescence and S₂←S₀-fluorescence excitation spectra for retinal in EPA at 77 K and DPH in a polyvinylbutyral film, point to the coincidence of the directions of absorption and emission oscillators. These oscillators are aligned along the major axis of the polyene molecule, and the longwave S₂←S₀-absorption band is formed only by one electronic¹B _u ⁺ ←¹A _g ⁻ -transition. The oscillators of shortwave S_a←S₀-absorption bands are aligned at an angle to the oscillators of the S₂←S₀-transitions, which is related to the distortions in the structure of molecules (β-carotene, lycopene) or, as in the case of DPH, to the influence of transitions localized on the orbitals of phenyl rings and polarized perpendicularly to the major axis of the molecule. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 1, pp. 69–74, January–February, 2000.     

The possibility of introducing additional states in the conduction band of YBa2Cu3Oy by Ca doping

Measurements of the temperature dependences of the resistivity and Seebeck coefficient S, as well as of the Hall coefficient R _H at T=300 K are reported for two series of ceramic Y_1−x Ca_xBa₂Cu₃O_y samples with oxygen contents in the initial sample close to stoichiometric and then lowered by annealing. It has been found that an increase in calcium content in the first series results in a drop of the critical temperature T _c , a weak variation of S (300 K), and an increase of R _H (300 K), whereas in the second series T _c increases, S (300 K) decreases, and R _H (300 K) remains practically constant. The S (T) relations acquire additional features with increasing doping level, which are not typical of the YBa₂Cu₃O_y system for other types of substitution. An analysis of the data obtained made in terms of the phenomenological band model permits a conclusion that calcium is capable of introducing additional states in the conduction band. Based on this assumption, we have succeeded in providing a qualitative explanation for the unusual features in the behavior of the transport coefficients and critical temperature in Y_1−x Ca_xBa₂Cu₃O_y. Fiz. Tverd. Tela (St. Petersburg) 40, 2145–2152 (December 1998)     

Resonance microwave photoresistance of a two-subband electron system at large filling factors

The microwave photoresistance of a double GaAs quantum well with two occupied size-quantization sub-bands E ₁ and E ₂ has been studied at the temperatures T = 1.6–4.2 K in the magnetic fields B < 0.5 T. The microwave photoresistance of such a system has been found to have a maximum amplitude when the maximum of the magneto-intersubband oscillations with the number k = (E ₂ − E ₁)ℏω_c coincides with the maximum or minimum of the ω/ω_c oscillations, where ω is the microwave frequency and ω_c is the cyclotron frequency. It has been shown that the resonance photoresistance that appears in the kth maximum of the magneto-intersubband oscillations is determined by the condition ℏω/(E ₂ − E ₁) = (j ± 0.2)/k, where k and j are positive integers.     

Mechanism of giant magnetoresistance in intermetallic compounds of rare-earth ions and actinides

Giant positive or negative magnetoresistance is calculated in a band model. The spectra of the band electrons in a two-sublattice antiferromagnetic intermetallic compound depend on the antiferromagnetism vector L(T,H). The metamagnetic transition to the ferromagnetic phase is accompanied by splitting with respect to the spin σ, displacement of the energy bands, and a decrease in the effective masses of the band electrons. This mechanism of giant negative magnetoresistance is also accompanied by an increase in the relaxation time τ_jσ. Scattering by chemical-bond fluctuations is considered as the main relaxation mechanism. Giant positive magnetoresistance results from a four-subband model of 4f and 5f intermetallic compounds. The electron effective masses m _jσ(J _jT ) of the (j,σ) bands increase with the mean angular momentum J _1T (T,H) of an ion in the jth sublattice of 4(5)f ions. The thermodynamics of such a four-sublattice model, the nonlinear magnetization and magnetoresistance curves, and the nonmonotonic dependence of the specific heat C _m(T,H) on the field H are calculated. Fiz. Tverd. Tela (St. Petersburg) 39, 1806–1814 (October 1997)     

Electrical properties of nickel-doped arsenic trisulphide

Results of temperature and frequency dependent a.c. conductivity of pure and nickel-doped a-As₂S₃ are reported. The a.c. conductivity of pure As₂S₃ obeys a well-known relationship: σ_ac ∝ω ^s. Frequency exponents is found to decrease with increasing temperature. Correlated barrier hopping (CBH) model successfully explains the entire behaviour of a.c. conductivity with respect to temperature and frequency for pure As₂S₃. But a different behaviour of a.c. conductivity has been observed for the nickel doped As₂S₃. At higher temperatures, distinct peaks have been observed in the plots of temperature dependence of a.c. conductivity. The frequency dependent behaviour of a.c. conductivity (σ_ac ∝ω ^s) for nickeldoped As₂S₃ is similar to pure As₂S₃ at lower temperatures. But at higher temperatures, ln σ_ac vs lnf curves have been found to deviate from linearity. Such a behaviour has been explained by assuming that nickel doping gives rise to some neutral defect states (D ^0′) in the band gap. Single polaron hopping is expected to occur between theseD ^0‘ andD ⁺ states. Furthermore, allD ⁺,D ^0′ pairs are assumed to be equivalent, having a fixed relaxation time at a given temperature. The contribution of this relaxation to a.c. conductivity is found to be responsible for the observed peak in the plots of temperature dependence of a.c. conductivity for nickel-doped As₂S₃. The entire behaviour of a.c. conductivity with respect to temperature and frequency has been explained by using CBH and “simple pair” models. Theoretical results obtained by using these models, have been found to be in agreement with the experimental results.     

Superconductivity, Seebeck coefficient, and band structure transformation in Y1−x CaxBa2Cu3−x CoxOy (x=0–0.3)

The temperature dependences of the resistivity and of the Seebeck coefficient S is studied in three series of Y_1−x Ca_xBa₂Cu_3−x Co_xO_y samples (x=0–0.3) differing in oxygen content. It was found that the critical temperature decreases for y≈7.0, and S(T=300 K) increases with doping, whereas oxygen deficiency results in a nonmonotonic variation of these quantities with increasing x. The band structure parameters have been determined from an analysis of the S(T) relations using a phenomenological theory of electron transport. It was found that an increase in x results in a gradual increase in band asymmetry, which is caused by calcium-induced creation of additional states in the band responsible for conduction in the normal phase. An analysis has shown that high impurity concentrations in oxygen-deficient Y_1−x Ca_xBa₂Cu_3−x Co_xO_y samples bring about an additional ordering of the structure, which may be caused by formation of a cobalt superlattice. It has also been shown that, in the case of Ca and Co codoping, the dependence of critical temperature on effective conduction-band width coincides with the universal correlation relation observed in the YBa₂Cu₃O_y system with single substitutions in various lattice sites. Fiz. Tverd. Tela (St. Petersburg) 41, 1363–1371 (August 1999)     

Electronic excitation and singlet-triplet coupling in uracil tautomers and uracil-water complexes

Electronic spectra of uracil in its diketo (lactam) form and five enol (lactim) tautomeric forms have been investigated by means of combined density functional and configuration interaction methods. We have simulated the effects of hydrogen bonding with a protic solvent by recomputing the spectrum of uracil in the presence of two, four, or six water molecules. Geometries of the electronic ground state and several low-lying excited states have been optimized. Spin-orbit coupling has been determined for correlated wavefunctions employing a non-empirical spin-orbit mean-field approach. In accord with experiment, we find the diketo tautomer to be the most stable one. The calculations confirm that the first absorption band arises from the ¹( π↦π^*) S ₀↦S ₂ excitation. The experimentally observed vibrational structure in this band originates from a breathing mode of the six ring. Complexation with water molecules is seen to cause a significant blue shift of n↦π^* excitations while leaving π↦π^* excitations nearly uninfluenced. Computed radiative lifetimes are presented for the experimentally known weak phosphorescence from the π↦π^* excited T₁ state. Among the uracil lactim tautomers, one is particularly interesting from a spectroscopic point of view. In this tautomer, the π↦π^* excitation gives rise to the S₁ state. Received 18 February 2002 / Received in final form 5 June 2002 Published online 13 September 2002     

Infrared ion dip and ultraviolet spectroscopy of 4-phenyl imidazole, its tautomer, 5-phenyl imidazole, and its multiply hydrated clusters

Mass-resolved resonant two photon ionisation (R2PI) and infrared ion dip spectra have been recorded for 4-phenylimidazole (4PI) and its singly and multiply hydrated clusters 4PI(H₂O)_{n = 0 - 4}, under supersonic expansion conditions. In the case of 4PI(H₂O)_0,1, it has also been possible to record infrared spectra in both the ground (S₀) and excited (S₁) states. Combining the experimental data with the results of ab initio calculations has led to the structural assignment of each cluster. In each case, the water molecules bind primarily to the NH site of the imidazole ring. Clusters with n≥ 2 incorporate linear water chains, in which the proton donating terminus bridges either to the π-electron system (n = 2) or to the >N: atom site (n = 3, 4) on the imidazole ring. Despite the creation of a “water wire”, connecting the donor and acceptor sites of imidazole, there is no evidence of proton transfer in either the ground or excited state. Received 20 December 2001 Published online 13 September 2002