Isotope effects in the vibrational spectrum of the SF<Subscript>6</Subscript> molecule

The IR absorption spectra of solutions of SF₆ in liquid argon are studied at a temperature of 93 K in the concentration interval 10^?5–10^?7 mole fractions. A sample with a natural abundance of isotopes and a monoisotope ³⁴SF₆ sample are studied. The frequencies, half-widths, and relative intensities of bands in the vibrational spectrum of all isotopomers of the molecule are determined. For the ³⁴SF₆ molecule, the ratio of integral absorption coefficients of fundamental bands A(ν₄)/A(ν₃)=0.07(6) is larger than ³²SF₆:A(ν₄)/A(ν₃)=0.66(4) for the ³²SF₆ molecule, which corresponds to the same signs of P′₃ and P′₄. The change in the intensity of the ν₂+ν₆ and ν₅+ν₆ bands upon isotopic substitution is explained by the change in the resonance contributions of due to the isotope shift of the ν₃ band.     

Dissimilarity between metallic-like transport in the dielectric spin density wave and field-induced spin density wave states in (TMTSF)<Subscript>2</Subscript>PF<Subscript>6</Subscript>

We report similarities and differences of the transport features in the spin density wave (SDW) and in the field-induced SDW (FISDW) phases of the quasi-one-dimensional compound (TMTSF)₂PF₆. As temperature decreases below ≈2 K, the resistance in both phases exhibits a maximum and a subsequent strong drop. However, the characteristic temperature of the R(T) maximum and its scaling behavior in different magnetic fields B are evidence that the nonmonotonic R(T) dependences have different origin in SDW and FISDW regions of the phase diagram. We also found that the borderline T₀(B, P) which divides the FISDW region of the P-B-T phase diagram into the hysteresis and nonhysteresis domains terminates in the N=1 subphase; the borderline thus has no extension to the SDW N=0 phase.     

Optical properties of mechanically compressed K<Subscript>2</Subscript>SO<Subscript>4</Subscript> crystals

The effect of a uniaxial mechanical compression (σ_m ≤ 100 bar) on the spectral dependences (300–800 nm) of the birefringence Δn _i and refractive indices n _i of K₂SO₄ crystals is studied. The electronic polarizabilities, refractions, and parameters (λ_0i , B _1i ) of ultraviolet oscillators of mechanically compressed crystals are calculated. It is shown that the dispersions of Δn _i(λ) and n _i(λ) are normal and sharply increase near the absorption edge. It is found that the uniaxial compression changes the value of the dispersions dΔn _i/dλ and dn _i/dλ rather than their character. It is ascertained that the simultaneous action of the compressions σ_x and σ_z, as well as of σ_y and σ_z, leads to the appearance of new isotropic states in the K₂SO₄ crystal, which manifests itself in the equality of corresponding birefringences. It is shown that the baric dependences n _i(σ) are determined by the change in the density of oscillators (～30%), by the shift of the absorption edge and effective band maximum and by the change in the oscillator strength (～70%).     

Adiabatic calorimetric study of the intense magnetocaloric effect and the heat capacity of (La<Subscript>0.4</Subscript>Eu<Subscript>0.6</Subscript>)<Subscript>0.7</Subscript>Pb<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript>

The temperature dependences of the intense magnetocaloric effect ΔT _AD(T, H) and the heat capacity C _p (T) of the (La_0.4Eu_0.6)_0.7Pb_0.3MnO₃ manganite are directly measured using adiabatic calorimetry. The experimental dependences ΔT _AD(T) are in satisfactory agreement with those calculated from the data on the behavior of the magnetization. The factors responsible for the absence of an anomaly in the experimental temperature dependence of the heat capacity C _p (T) in the range of the magnetic phase transition are discussed.     

Absorption spectra of some radiation-doped A<Subscript>3</Subscript>B<Subscript>5</Subscript> compounds

Temperature dependences of the absorption coefficient in A₃B₅ crystals before and after irradiation by electrons with an energy of 6 MeV and a dose of Ф = 2 × 10¹⁷ electron/cm² are studied. A low-lying E_v + 0.4 eV center of a nonimpurity origin is found in both undoped GaAs crystals and those doped with various impurities (Te, Zn, Sn, Ga_1–xIn_xAs, InP, and InP〈Fe〉).     

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.     

A theoretical investigation of structural,mechanical, electronic and thermoelectric properties of orthorhombic CH<Subscript>3</Subscript>NH<Subscript>3</Subscript>PbI<Subscript>3</Subscript>

The structural, mechanical, electronic and thermoelectric properties of the low temperature orthorhombic perovskite phase of CH₃NH₃PbI₃ have been investigated using density functional theory (DFT). Elastic parameters bulk modulus B, Young’s modulus E, shear modulus G, Poisson’s ratio ν and anisotropy value A have been calculated by the Voigt–Reuss–Hill averaging scheme. Phonon dispersions of the structure were investigated using a finite displacement method. The relaxed system is dynamically stable, and the equilibrium elastic constants satisfy all the mechanical stability criteria for orthorhombic crystals, showing stability against the influence of external forces. The lattice thermal conductivity was calculated within the single-mode relaxation-time approximation of the Boltzmann equation from first-principles anharmonic lattice dynamics calculations. Our results show that lattice thermal conductivity is anisotropic, and the corresponding lattice thermal conductivity at 150 K was found to be 0.189, 0.138, and 0.530 Wm^?1K^?1 in the a, b, and c directions. Electronic structure calculations demonstrate that this compound has a DFT direct band gap at the gamma point of about 1.57 eV. The electronic transport properties have been calculated by solving the semiclassical Boltzmann transport equation on top of DFT calculations, within the constant relaxation time approximation. The Seebeck coefficient S is almost constant from 50 to 150 K. At temperatures 100 and 150 K, the maximal figure of merit is found to be 0.06 and 0.122 in the direction of the c-axis, respectively.     

Thermophysical studies of the phase transitions in (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>NbOF<Subscript>6</Subscript> crystals

The thermophysical properties of oxyfluoride (NH₄)₃NbOF₆ were studied in detail over wide ranges of temperatures and pressures. At atmospheric pressure, a sequence of four structural phase transitions was established with the following changes in entropy: ΔS ₁ = Rln 2.7, δS ₂ = Rln38.3, ΔS ₃ = 0.08R, and ΔS ₄ = 0.17R. An external hydrostatic pressure was found to narrow the region of existence of the initial cubic phase. A triple point was detected in the p-T diagram; at a pressure above 0.07 GPa, the transition between the tetragonal and monoclinic phases occurs through a distorted high-pressure phase.     

Electron-impact excitation of barium atoms from metastable 5 <Superscript>3</Superscript><Emphasis Type="Italic">D</Emphasis><Subscript><Emphasis Type="Italic">J</Emphasis></Subscript> states

The excitation of spectral transitions of barium atoms from the 5³ D _J states by electron impact has been studied experimentally. The absolute values of the interaction cross sections and their energy dependences have been determined. The results obtained have been compared with theoretical calculations both by the classical Born approximation method and by the R-matrix method using the multiconfiguration Hartree-Fock wave functions of a target.     

Structural and magnetic phase transformations in the BiFeO<Subscript>3</Subscript>-CaFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> system

The crystal structure and magnetic properties of the Bi_{1 ? x} Ca _x Fe_{1 ? x/2}Nb _x/2O₃ system were studied. It is shown that, at x ≤ 0.15, the unit-cell symmetry of solid solutions is rhombohedral (space group R3c). Solid solutions with x ≥ 0.3 have an orthorhombic unit cell (space group Pbnm). The rhombohedral compositions are antiferromagnetic, while the orthorhombic compositions exhibit a small spontaneous magnetization due to Dzyaloshinski?-Moriya interaction. In CaFe_0.5Nb_0.5O₃, the Fe³⁺ and Nb⁵⁺ ions are partially ordered and the unit cell is monoclinic (space group P2₁/n). In the concentration range 0.15 < x < 0.30, a two-phase state (R3c + Pbnm) is revealed.     

Lattice dynamics of BiFeO<Subscript>3</Subscript> under hydrostatic pressure

The vibrational frequencies of the BiFeO₃ crystal lattice in the cubic phase (Pm3m) and the rhombohedral paraelectric phase (R3c) are calculated in terms of the ab initio model of an ionic crystal with the inclusion of the dipole and quadrupole polarizabilities. In the ferroelectric phase with the symmetry R3c, the calculated spontaneous polarization of 136 μC cm^?2 agrees well with the experimental data. The dependences of the unit cell volume, the elastic modulus, and the vibrational frequencies on the pressure are calculated. It is found that the frequency of an unstable ferroelectric mode in both the cubic (Pm3m) and rhombohedral (R3c) phases are almost independent of the applied pressure, in contrast to classical ferroelectrics with a perovskite structure, where the ferroelectric instability is very sensitive to a variation in the pressure.     

Exchange Bias in Layered GdBaCo<Subscript>2</Subscript>O<Subscript>5.5</Subscript> Cobaltite

It is established that excess oxygen content δ influences the exchange bias (EB) in layered GdBa-Co₂O_{5 + δ} cobaltite. The EB effect arises in p-type (δ > 0.5) cobaltite and disappears in n-type (δ < 0.5) cobaltite. The main parameters of EB in GdBaCo₂O_5.52(2) polycrystals are determined, including the field and temperature dependences of EB field H _EB , blocking temperature T _B , exchange coupling energy J _i of antiferromagnet–ferromagnet (AFM–FM) interface, and dimensions of FM clusters. The training effect inherent in systems with EB has been studied. The results are explained in terms of exchange interaction between the FM and AFM phases. It is assumed that the EB originates from the coexistence of Co³⁺ and Co⁴⁺ ions that leads to the formation of monodomain FM clusters in the AFM matrix of cobaltite.     

Electron transport,penetration depth,and the upper critical magnetic field in ZrB<Subscript>12</Subscript> and MgB<Subscript>2</Subscript>

We report on the synthesis and measurements of the temperature dependences of the resistivity ρ, the penetration depth λ, and the upper critical magnetic field H_c2, for polycrystalline samples of dodecaboride ZrB₁₂ and diboride MgB₂. We conclude that ZrB₁₂ behaves as a simple metal in the normal state with the usual Bloch-Grüneisen temperature dependence of ρ(T) and with a rather low resistive Debye temperature T_R = 280 K (to be compared to T_R = 900 K for MgB₂). The ρ(T) and λ(T) dependences for these samples reveal a superconducting transition in ZrB₁₂ at T_c = 6.0 K. Although a clear exponential λ(T) dependence in MgB₂ thin films and ceramic pellets was observed at low temperatures, this dependence was almost linear for ZrB₁₂ below T_c/2. These features indicate an s-wave pairing state in MgB₂, whereas a d-wave pairing state is possible in ZrB₁₂. In disagreement with conventional theories, we found a linear temperature dependence, of H_c2(T) for ZrB₁₂ (H_c2(0) = 0.15 T).     

Elastic properties of La<Subscript>0.82</Subscript>Ca<Subscript>0.18</Subscript>MnO<Subscript>3</Subscript> single crystal

The temperature dependences of the velocity of longitudinal sound waves and the internal friction in a La_0.82Ca_0.18MnO₃ single crystal with the Curie temperature T _C = 181 K have been studied. As temperature decreases, the single crystal is shown to undergo the transition from the pseudocubic O* to the Jahn–Teller O’ phase at T ~ 254 K and the reverse transition from O’ to O* phase at T ~ 84 K. The velocity of sound and the internal friction in the O’ phase are found to be significantly smaller than those in the O* phase.     

X-ray study of [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> at low temperatures

The unit cell parameters a, b, and c of [N(CH₃)₄]₂ZnCl₄ have been measured by x-ray diffraction in the temperature range 80–293 K. Temperature dependences of the thermal expansion coefficients α_a, α_b, and α_c along the principal crystallographic axes and of the unit cell thermal expansion coefficient α_V were determined. It is shown that the a=f(T), b=f(T), and c=f(T) curves exhibit anomalies in the form of jumps at phase transition temperatures T₁=161 K and T₂=181 K and that the phase transition occurring at T₃=276 K manifests itself in the a=f(T) and b=f(T) curves as a break. A slight anisotropy in the coefficient of thermal expansion of the crystal was revealed. The phase transitions occurring at T₁=161 K and T₂=181 K in [N(CH₃)₄]₂ZnCl₄ were established to be first-order.     

Genesis of the anomalous Hall effect in CeAl<Subscript>2</Subscript>

The Hall coefficient R _H , resistivity ρ, and Seebeck coefficient S of the CeAl₂ compound with fast electron density fluctuations were studied in a wide temperature range (from 1.8 to 300 K). Detailed measurements of the angular dependences R _H (? T, H≤70 kOe) were performed to determine contributions to the anomalous Hall effect and study the behavior of the anomalous magnetic R _H ^am and main R _H ^a components of the Hall signal of this compound with strong electron correlation. The special features of the behavior of the anomalous magnetic component R _H ^am were used to analyze the complex magnetic phase diagram H-T determined by magnetic ordering in the presence of strong spin fluctuations. An analysis of changes in the main contribution R _H ^a (H, T) to the Hall effect made it possible to determine the complex activation behavior of this anomalous component in the CeAl₂ intermetallic compound. The results led us to conclude that taking into account spin-polaron effects was necessary and that the Kondo lattice and skew-scattering models were of very limited applicability as methods for describing the low-temperature transport of charge carriers in cerium-based intermetallic compounds. The effective masses and localization radii of manybody states in the CeAl₂ matrix were estimated to be (55–90)m₀ and 6–10 Å, respectively. The behaviors of the parameters R _H , S, and ρ were jointly analyzed. The results allowed us to consistently describe the transport coefficients of CeAl₂.     

Refractometry of mechanically compressed (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>SO<Subscript>4</Subscript> crystals

The effect of uniaxial mechanical pressure σ _m ≤ 150 bar on the spectral (300–800 nm) dependence of the birefringerence Δn _i and refractive indices n _i of (NH₄)₂SO₄ crystals has been investigated. It is shown that the dispersion of n _i (λ) and Δn _i (λ) is normal and sharply increases with approach to the absorption edge. It is established that uniaxial pressure does not change the character of the dispersions dn _i /dλ and dΔn _i /dλ and only affects their magnitudes. It is shown that the increase in the refractive indices under uniaxial stress is mainly due to the increase in the refraction caused by the increase in the band gap and long-wavelength shift of the UV absorption band maximum.     

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.     

Long-time relaxation phenomena in Pb<Subscript>0.94</Subscript>Ba<Subscript>0.06</Subscript>Sc<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> (PBSN-6) single crystals

Long-time polarization relaxation in the temperature range where PBSN-6 single crystals reside in the relaxor state was studied. An analysis of the time dependence of the permittivity ε′(t) performed at measuring frequencies from 1 Hz to 1 kHz in weak electric fields E₀ showed that the relaxation (or freezing) times derived by extrapolating relations of the type ε′(t) ～ log(t/t₀) and ε′(t) ～ exp{?[ln(t/t₀)]_β} range from 10⁸ to 10¹¹ min and depend substantially on the bias voltage applied to the sample. A study of the pattern of the dielectric response in moderate and strong infralow-frequency fields revealed that, after a sample was maintained under a bias lower than the coercive force, it no longer exhibited the additional anomalies in the amplitude dependences of the effective loss tangent tan_eff(E₀) than were observed in a thermally recuperated sample.     

Electron gas induced in SrTiO<Subscript>3</Subscript>

This mini-review is dedicated to the 85th birthday of Prof. L.V. Keldysh, from whom we have learned so much. In this paper, we study the potential and electron density depth profiles in surface accumulation layers in crystals with a large and nonlinear dielectric response such as SrTiO₃ (STO) in the cases of planar, spherical, and cylindrical geometries. The electron gas can be created by applying an induction D₀ to the STO surface. We describe the lattice dielectric response of STO using the Landau–Ginzburg free energy expansion and employ the Thomas–Fermi (TF) approximation for the electron gas. For the planar geometry, we arrive at the electron density profile n(x) ∝ (x + d)^–12/7, where d ∝ D₀^–12/7. We extend our results to overlapping electron gases in GTO/STO/GTO heterojunctions and electron gases created by spill-out from NSTO (heavily n-type doped STO) layers into STO. Generalization of our approach to a spherical donor cluster creating a big TF atom with electrons in STO brings us to the problem of supercharged nuclei. It is known that for an atom with a nuclear charge Ze where Z > 170, electrons collapse onto the nucleus, resulting in a net charge Zn < Z. Here, instead of relativistic physics, the collapse is caused by the nonlinear dielectric response. Electrons collapse into the charged spherical donor cluster with radius R when its total charge number Z exceeds the critical value Z_c ≈ R/a, where a is the lattice constant. The net charge eZ_n grows with Z until Z exceeds Z* ≈ (R/a)^9/7. After this point, the charge number of the compact core Z_n remains ≈ Z*, with the rest Z* electrons forming a sparse TF atom with it. We extend our studies of collapse to the case of long cylindrical clusters as well.