Optical absorption and photoconductivity of MnGaInS<Subscript>4</Subscript> single crystals in polarized light

The results of studying optical-absorption and spectral curves of photoconductivity in MnGaInS₄ single crystals are presented for two light polarizations (E || C and E ⊥ C). The intrinsic absorption edge and the band-gap width of MnGaInS4 single crystals in polarized light are determined. The anisotropy of optical absorption and photoconductivity spectrum of MnGaInS₄ single crystals is observed. It is suggested that the polarization splitting of the absorption edge is related to the splitting of the MnGaInS₄ valence band.     

Optical 4<Emphasis Type="Italic">f</Emphasis>-4<Emphasis Type="Italic">f</Emphasis> transitions in multiferroic HoMnO<Subscript>3</Subscript>

In the absorption spectra of the hexagonal single-crystal manganite HoMnO₃ in the paramagnetic ferroelectric state, lines near 1.1 and 2.0 μm were observed associated with the transitions ⁵ I ₈ → ⁵ I ₆ and ⁵ I ₈ → ⁵ I ₇, respectively, within the 4f ¹⁰ configuration of the Ho³⁺ ion. At T = 80 K, to the ⁵ I ₈ → ⁵ I ₇ transition corresponds one band at 1.9 μm for both polarizations E ∥ c and E ⊥ c. As the temperature increases from 80 to 293 K, a low-energy band with a peak at 2.04 μm for E ⊥ c and a peak at 2.07 μm for E ∥ c arises associated with transitions from an excited Stark level of the ground ⁵ I ₈ multiplet to the Stark levels of the ⁵ I ₇ multiplet and with an increase in the population of the initial Stark level, the energy of which is ～100 K.     

High-frequency properties of KNiPO<Subscript>4</Subscript> in alternating magnetic and electric fields

The dependences of the antiferromagnetic resonance frequencies on the constant magnetic field H and constant electric field E are calculated for a KNiPO₄ crystal with spontaneous electric polarization and antiferromagnetic order. It is demonstrated that the KNiPO₄ crystal is characterized by an exchange-enhanced effect of the electric field E on the antiferromagnetic resonance frequencies. This effect is not revealed in the magnetoelectric materials studied earlier. It is established that oscillations of both magnetization and electric polarization exhibit resonance response at antiferromagnetic resonance frequencies. The expressions for these responses in alternating magnetic and electric fields are presented.     

Effect of a Rare-Earth Ion on the Structural Instability in RFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> Crystals

The dynamics of the crystal lattice of RFe₃(BO₃)₄ (R = Pr, Nd, Sm, Gd, Tb, Dy, and Ho) compounds in the high-symmetry R32 phase has been calculated. Significant changes in spectra of compounds with various rare-earth ions have been obtained only near the edge Λ point of the Brillouin zone (qΛ = 1/3(?2b₁ + b₂ + b₃, where b₁, b₂, and b₃ are the reciprocal lattice vectors) for acoustic oscillation branches. A decrease in the frequency of an acoustic mode at the point Λ has been revealed in all studied compounds. This frequency depends on the type of rare-earth ion and decreases from a compound with Pr to a compound with Ho down to imaginary values. Such a behavior of the frequency of the unstable acoustic mode is in good agreement with experimental data on the dependence of the temperature of the R32 → P3₁21 structural phase transition on the type of rare-earth ion in ferroborates.     

Interrelation of anisotropy of magnetic properties and magnetodielectric effect in a Cu<Subscript>3</Subscript>B<Subscript>2</Subscript>O<Subscript>6</Subscript> single crystal

The effect of an external magnetic field on permittivity has been studied in a Cu₃B₂O₆ single crystal with a layered structure in the direction perpendicular to layers (bc-planes). It has been found that the appreciable magnetodielectric effect in the temperature range below the Néel temperature (≈10 K) takes place only at one magnetic field orientation H and one crystallographic direction, i.e., H || b. Such “selectivity” of the magnetodielectric effect correlates with the anisotropic behavior of magnetic properties of the crystal.     

Influence of the ground state of the Pr<Superscript>3+</Superscript> ion on magnetic and magnetoelectric properties of the PrFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> multiferroic

The magnetic, magnetoelectric, and magnetoelastic properties of a PrFe₃(BO₃)₄ single crystal and the phase transitions induced in this crystal by the magnetic field are studied both experimentally and theoretically. Unlike the previously investigated ferroborates, this material is characterized by a singlet ground state of the rare-earth ion. It is found that, below T _N = 32 K, the magnetic structure of the crystal in the absence of the magnetic field is uniaxial (l ∥ c), while, in a strong magnetic field H ∥ c (H _cr ～ 43 kOe at T = 4.2 K), a Fe³⁺ spin reorientation to the basal plane takes place. The reorientation is accompanied by anomalies in magnetization, magnetostriction, and electric polarization. The threshold field values determined in the temperature interval 2–32 K are used to plot an H-T phase diagram. The contribution of the Pr³⁺ ion ground state to the parameters under study is revealed, and the influence of the praseodymium ion on the magnetic and magnetoelectric properties of praseodymium ferroborate is analyzed.     

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.     

Electron paramagnetic resonance of Cr<Superscript>3+</Superscript>-Li<Superscript>+</Superscript> centers in (Cr,Li): Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> synthetic forsterite

Synthetic single crystals of chromium-and lithium-doped forsterite, namely, (Cr,Li): Mg₂SiO₄, are studied using electron paramagnetic resonance spectroscopy. It is revealed that, apart from the known centers Cr³⁺(M1) and Cr³⁺(M2) (with local symmetries C_i and C_s, respectively), these crystals involve two new types of centers with C₁ symmetry, namely, Cr³⁺(M1)′ and Cr³⁺(M2)′ centers. The standard parameters D and E in a zero magnetic field [zero-field splitting (ZFS) parameters expressed in GHz] and principal components of the g tensor are determined as follows: D=31.35, E=8.28, and g=(1.9797, 1.9801, 1.9759) for Cr³⁺(M1)′ centers and D=15.171, E=2.283, and g=(1.9747, 1.9769, 1.9710) for Cr³⁺(M2)′ centers. It is found that the lowsymmetric effect of misalignment of the principal axes of the ZFS and g tensors most clearly manifests itself (i.e., its magnitude reaches 19°) in the case of Cr³⁺(M2)′ centers. The structural models Cr³⁺(M1)-Li⁺(M2) and Cr³⁺(M2)-Li⁺(M1) are proposed for the Cr³⁺(M1)′ and Cr³⁺(M2)′ centers, respectively. The concentrations of both centers are determined. It is demonstrated that, upon the formation of Cr³⁺-Li⁺ ion pairs, the M1 position for chromium appears to be two times more preferable than the M2 position. Reasoning from the results obtained, the R₁ line (the ²E → ⁴A₂ transition) observed in the luminescence spectra of (Cr,Li): Mg₂SiO₄ crystals in the vicinity of 699.6 nm is assigned to the Cr³⁺(M1)′ center.     

Thermodynamics of the frustrated J<Subscript>1</Subscript>-J<Subscript>2</Subscript> Heisenberg ferromagnet on the body-centered cubic lattice with arbitrary spin

We use the spin-rotation-invariant Green’s function method as well as thehigh-temperature expansion to discuss the thermodynamic properties of the frustratedspin-S J ₁-J ₂ Heisenbergmagnet on the body-centered cubic lattice. We consider ferromagnetic nearest-neighborbonds J ₁<0 and antiferromagnetic next-nearest-neighbor bonds J ₂ ≥ 0 andarbitrary spin S. We find that the transition point\hbox{$J_2^c$}J2cbetween the ferromagnetic ground state and theantiferromagnetic one is nearly independent of the spin S, i.e., it is very closeto the classical transition point\hbox{$J_2^{c,{\rm clas}}= \frac{2}{3}|J_1|$}J2c,clas=23|J1|. At finite temperatures we focus on the parameterregime\hbox{$J_2<J_2^c$}J2<J2cwith a ferromagnetic ground-state. We calculate theCurie temperature T _C (S, J ₂)and derive an empirical formula describing the influence of the frustration parameterJ ₂ and spin S on T _C . We find that theCurie temperature monotonically decreases with increasing frustration J ₂, where veryclose to\hbox{$J_2^{c,{\rm clas}}$}J2c,clasthe T _C (J ₂)-curveexhibits a fast decay which is well described by a logarithmic term\hbox{$1/\textrm{log}(\frac{2}{3}|J_1|-J_{2})$}1/log(23|J1|?J2). To characterize the magnetic ordering below and aboveT _C , we calculate thespin-spin correlation functions ?S ₀ S _R ?, the spontaneous magnetization, the uniform static susceptibilityχ ₀ as well as the correlation lengthξ.Moreover, we discuss the specific heat C _V and the temperaturedependence of the excitation spectrum. As approaching the transition point\hbox{$J_2^c$}J2csome unusual features were found, such as negativespin-spin correlations at temperatures above T _C even though theground state is ferromagnetic or an increase of the spin stiffness with growingtemperature.     

Magnetic structure of the quasi-one-dimensional frustrated antiferromagnet LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> with Spin <Emphasis Type="Italic">S</Emphasis> = 1/2

The magnetic properties of LiCu₂O₂ single-crystal samples without twinning are investigated using electron spin resonance and nuclear magnetic resonance spectroscopy. The experimental results obtained are described in terms of the model of a planar spiral antiferromagnet for the orientation of the magnetic field H ‖ b or H ‖ c and the model of a collinear spin-modulated antiferromagnet for the orientation of the static magnetic field H ‖ a.     

NMR study of topological insulator Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> in a wide temperature range

NMR studies of ¹²⁵Te in the topological insulator bismuth telluride Bi₂Te₃ in a wide temperature range from room temperature to 12.5 K are performed. The pulsed NMR spectrometer Bruker Avance 400 is applied. The NMR spectra are obtained for the powder from Bi2Te3 single crystal and monocrystalline plates with the orientations c || B and c ⊥ B. At room temperature, the spectra consist of two lines related to two nonequivalent positions of tellurium nuclei Te1 and Te2. The parameters of the NMR frequency shift tensor are found from the powder spectrum. The temperature dependences of the spectra for the powder and plates with the orientation c ⊥ B agree with each other. The line shift with decreasing temperature is explained by the reduction of the Knight shift. The thermal activation energy of charge carriers is estimated. The spectra for the plates with the orientation c || B demonstrate peculiar behavior below 91 K. The spin-lattice relaxation time for the powder and monocrystalline plates with both orientations at room temperature is measured.     

NMR studies of single crystals of the topological insulator Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> at low temperatures

A powder sample and single-crystal plates of the topological insulator Bi₂Te₃ have been investigated using the ¹²⁵Te NMR method at room temperature and at low temperatures in the range from 12.5 to 16.5 K. The NMR spectra of the single-crystal plates have been studied in the orientation where the crystallographic axis c is directed parallel or perpendicular to the magnetic field. The spectra have been obtained by means of recording spin-echo signals and plotting their envelopes. It has been shown that the NMR spectra for the bismuth telluride powder and plates with the orientation c ⊥ B consist of two lines, which are presumably attributed to tellurium nuclei in two crystallographic positions in the bulk of the sample. The position and shape of the lines are determined by the chemical shift and the Knight shift. For the orientation of the plates c || B, the spectrum contains an additional component in the high-frequency region, which cannot appear due to the angular dependence of the line shifts caused by tellurium nuclei in the bulk of the topological insulator. At a low temperature, the additional line dominates in the spectrum.     

V<Subscript>52</Subscript>O<Subscript>64</Subscript> tetragonal superstructure of cubic vanadium monoxide with vacancies in the metal sublattice

The atom-vacancy ordering of cubic vanadium monoxide VO_1.29, which has basis cubic structure B1 and structural vacancies in the metal sublattice, has been studied using the x-ray diffraction method. It has been shown that the formation of the tetragonal (space group I4₁/amd) ordered phase V₅₂O₆₄ of cubic vanadium monoxide VO_y proceeds as a first-order phase transition through the disorder-order channel including 22 nonequivalent superstructure vectors of four stars {k ₁₀}, {k ₄}, {k ₃}, and {k ₂}. The distribution function of the vanadium atoms in the V₅₂O₆₄ tetragonal superstructure has been calculated.     

Thermophysical study of structural phase transitions in Na<Subscript>0.95</Subscript>Li<Subscript>0.05</Subscript>NbO<Subscript>3</Subscript> solid solution

Temperature dependences of specific heat C_p(T) and coefficient of thermal expansion ;(T) for Na_0.95Li_0.05NbO₃ sodium-lithium niobate ceramic samples are investigated in the temperature range of 100–800 K. The C_p(T) and α(T) anomalies at T₃ = 310 ± 3 K, T₂ = 630 ± 8 K, and T₁ = 710 ± 10 K are observed, which correspond to the sequence of phase transitions N ? Q ? S(R) ? T2(S). The effect of heat treatment of the samples on the sequence of structural distortions was established. It is demonstrated that annealing of the samples at 603 K leads to splitting of the anomaly corresponding to the phase transition Q → R/S in two anomalies. After sample heating to 800 K, the only anomaly is observed in both the C_p(T) and ;(T) dependence. Possible mechanisms of the observed phenomena are discussed.     

Anisotropy of magnetic properties of Sm<Subscript>0.55</Subscript>Sr<Subscript>0.45</Subscript>MnO<Subscript>3</Subscript> single crystals

Anisotropy of the magnetic properties of Sm_0.55Sr_0.45MnO₃ single crystals has been studied. A significant increase in the antiferromagnetic component of magnetization in the case of orientation of an external magnetic field H close to the c axis has been found. Magnetization for a field lying in the ab plane seems typical of a ferromagnet. Anisotropy of susceptibility reaches 2.2 in weak fields and nearly vanishes at H > 1 T.     

Zeeman effect and stark splitting of the electronic states of the rare-earth ion in the paramagnetic terbium garnets Tb<Subscript>3</Subscript>Ga<Subscript>5</Subscript>O<Subscript>12</Subscript> and Tb<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>

The Zeeman effect in the ⁷ F ₆ → ⁵ D ₄ absorption band of the Tb³⁺ ion in the paramagnetic garnets Tb₃Ga₅O₁₂ and Tb₃Al₅O₁₂ was studied. The field dependences of the Zeeman splitting of some absorption lines are found to exhibit unusual behavior: as the magnetic field increases, the band splitting decreases rather than increases. Symmetry analysis relates these lines to 4f → 4f electron transitions of the doublet-quasi-doublet or quasi-doublet-doublet type, for which the field dependences of the splitting differ radically from the well-known field dependences of the Zeeman splitting for quasi-doublet-quasi-doublet or quasi-doublet-singlet transitions in a longitudinal magnetic field.     

Formation of the incommensurate ordered phase in TaC<Subscript>y</Subscript> carbide

Structural neutron diffraction studies indicate that only one ordered phase arises after the disorder-order transition in nonstoichiometric cubic tantalum carbide TaC_y. This phase arises in the composition range y = 0.79–0.89 due to long-term annealing with a decrease in temperature from 1600 to 300 K. It is incommensurate in the [1–11]_B1 direction, but it is close to commensurate M₆C₅ structures (C2/m and P3₁ space groups) in mutual arrangement of atoms and vacancies in nonmetallic (1–11)_B1 planes. The disorder-order transition channel that is associated with the formation of the incommensurate superstructure in TaC_y carbide includes two arms k ₅ ⁽⁶⁾ ≈ 0.473b₂ and k ₅ ⁽⁵⁾ = ?k ₅ ⁽⁶⁾ of the {k₅} star and arms of the {k₄} and {k₃} stars. The translation period of the incommensurate phase in the [1–11]_B1 direction is 8.9–9.1 nm, which is larger than that in the commensurate phase M₆C₅ by a factor of about 18.     

Ordering of the lowest tungsten carbide W<Subscript>2</Subscript>C

Atomic-vacancy ordering of the lowest tungsten carbide W₂C with the basis hexagonal structure of the L’3 type is analyzed by neutron and x-ray diffraction studies. It is found that the trigonal phase ?-W₂C (space group \(P\bar 3\) 1m) is the only ordered phase in the temperature range from ～2700 to 1370 K. The disorder-order phase transition channel associated with the formation of the trigonal ?-W₂C phase is found to include three superstructure vectors k ₁₅ ⁽¹⁾ , k ₁₅ ⁽²⁾ , and k ₁₇ ⁽¹⁾ of two stars {k ₁₅} and {k ₁₇}. The distribution function of the carbon atoms in the trigonal ?-W₂C superstructure is calculated.     

High-temperature deformation and specific features of dislocation structure of Ti<Subscript>3</Subscript>Al

The transmission electron microscopy was used to examine the dislocation structure of intermetallic Ti₃Al after deformation at temperatures T = 1073–1273 K. It is established that its microstructure contains mobile 2c + a and superdislocations. Possible models describing the destruction of barriers associated with 2c + a superdislocations in pyramidal planes are discussed using the results of computer simulation of the superdislocation core structure in Ti₃Al.     

A Water-Soluble Fluorescent Probe for SO<Subscript>2</Subscript> Derivatives in Aqueous Solution and Serum Based on Phenanthroimidazole Dye

A water-soluble fluorescent SO₂ derivatives probe PI-SO ₂ based on a phenanthroimidazole dye, and a sensitive SO₂ recognition site, aldehyde was constructed. The probe PI-SO ₂ exhibits desirable properties such as high sensitivity, high selectivity and good water-solubility. Significantly, we have demonstrated that the probe PI-SO ₂ is suitable for rapidly fluorescence detecting of SO₂ derivatives in aqueous solution and serum. The application of the novel probe PI-SO ₂ proved that it was not only a useful tool for the detection of SO₂ derivatives in vitro, but also a potential assay for investigating the effects of SO₂ derivatives, and demonstrating its value in practical applicationin of complex biological samples.