The transverse dielectric properties of KH2PO4

We have measured the transverse dielectric constant of KH₂PO₄ crystal from liquid N₂ to room temperatures. Extending the Blinc-de Gennes' model in conjunction with a cluster approximation leads to a new independent determination of the Slater-Takagi parameters and improves significantly the fit of the model to the data.     

Specific heat of DyVO4 with applied magnetic field

The specific heat of DyVO₄ was measured as a function of temperature for various applied magnetic fields up to 8T. A quantitative analysis was undertaken using the so-called “compressible Ising model”. The general experimental behaviour was reproduced but discrepancies were observed for the highest fields, presumably due to the importance of short range order interactions which are not satisfactorily taken into account by the model.     

Interpretation of the specific heat at the Jahn-Teller phase transition in DyVO4 using a “compressible” Ising model

The specific heat at the Jahn-Teller phase transition in DyVO₄ is too sharply peaked to be explained by simple mean-field theory, but is very well described by using a mean-field model in which the effective interaction increases upon ordering according to J′=J₀′(1+ζ〈σ^z〉²) where ζ is an adjustable parameter.     

Jahn-Teller band transition in La3S4 and La3Se4

La₃S₄ and La₃Se₄ undergo a cubic to tetragonal phase transformation at a temperature of 103 and 70 K respectively, the c/a ratio is 0.984 for La₃S₄ and 0.987 for La₃Se₄. In these compounds the conduction electron Fermi energy happens to be close to a band structure anomaly which drives the phase transition. We find some indication, that the anomaly might be of ?-type.     

Jahn-Teller effect in crystals: Optical response function and vibronic states

We present a method for evaluating the optical spectrum of a Jahn-Teller centre in a crystal. We are able to obtain an approximated, but not perturbative, expression for the optical response function of the system in the weak coupling case. All cases of electronic degeneracy are treated together. The general formulae giving the zero-phonon line and the one- and two-phonon bands are obtained in the two cases of Jahn-Teller interaction acting when the electron is in the ground or in an excited level. In particular, the contribution of the vibronic states as peaks in the one-phonon band is explicitly shown.     

Electronic and vibronic spectra of Pr in LiYF4

The polarized absorption and fluorescence spectra of Pr³⁺ in single crystals of LiYF₄ having the scheelite structure have been investigated and assignments made on the basis of S₄ site symmetry. Strong vibronic coupling associated with the ³H₄→³H₅, ¹D₂ transitions in absorption and the ³P₀→³H_4,6 transitions in fluorescence was observed. Using selection rules for vibronic coupling and the known k = 0 phonons, these “extra” features of the spectrum can be accounted for in polarization and frequency.     

Features of the behavior of longitudinal static and dynamic dielectric, piezoelectric, and elastic characteristics of KH2PO4 and NH4H2PO4 crystals

Along with their electromechanical coupling coefficients, the longitudinal dielectric, piezoelectric and elastic characteristics in ferroelectric KH₂PO₄ and antiferroelectric NH₄H₂PO₄ crystals are calculated using a modified proton ordering model that considers piezoelectric coupling and the four-particle cluster approximation. The possibility of detecting piezoactivity in solid solutions of K_{1 − x} (NH₄)xH₂PO₄ is substantiated.     

Jahn-Teller transition in Al doped LiMn2O4 spinel

Al-doped lithium manganese spinels, with starting composition Li_1.02Al_xMn_1.98−xO₄ (0.00<x≤0.06), are investigated to determine the influence of the Al³⁺ doping on the Jahn-Teller (J-T) cooperative transition temperature T_J-T. X-ray powder diffraction (XRPD), nuclear magnetic resonance, electron paramagnetic resonance, conductivity and magnetic susceptibility data are put into relation with the tetrahedral and octahedral occupancy fraction of the spinel sites and with the homogeneous distribution of the Al³⁺ ions in the spinel phase. It is observed that Al³⁺ may distribute between the two cationic sublattices. The J-T distortion, associated with a drop of conductivity near room temperature in the undoped sample, is shifted towards lower temperature by very low substitution. However, for x>0.04 T_J-T it increases with increasing x, as clearly evidenced in low temperature XRPD observations. A charge distribution model in the cationic sublattice, for Al substitution, is proposed to explain this peculiar behavior.     

Effects of applied magnetic fields on the magnetic structure of DyVO4

The influence of a magnetic field on the magnetic structure of DyVO₄ has been studied on a single crystal at 1.8 K in fields up to 15 kG. At 3.0 kG we observed a domain reorientation along the applied magnetic field. A spin-flip transition to a ferromagnetic state could not be observed within our experimental range.     

Theory of optical spectra of impurity centres in crystals: general consideration of quadratic vibronic coupling

A method is proposed for the calculation of the spectra of the multiphonon transitions caused by the quadratic vibronic coupling with a phonon continuum. In the method, the time evolution of the final state is described by the path integrals. By applying the Stratonovich-Hubbard identity, the quadratic coupling is presented as the fluctuating linear coupling; the latter is calculated by the Lax method. As a result, the problem is reduced to the calculation of the determinants of matrices, the elements of which are given by the pair correlation functions of the contributing configurational coordinates. The method has been verified for the case of two mixed modes. Numerical calculations have also been made for a modified Debye model.     

Low-temperature high-resolution VUV spectroscopy of Ce doped LiYF4, LiLuF4 and LuF3 crystals

For LiYF₄:Ce³⁺, LiLuF₄:Ce³⁺ and LuF₃:Ce³⁺ crystals UV/visible emission and time-resolved VUV/UV excitation spectra were recorded at liquid helium temperature with spectral resolution of 0.1 nm for excitation spectra and better than 0.3 nm for emission spectra. Well resolved fine structures due to zero-phonon lines were clearly observed in both excitation and emission spectra for LiYF₄:Ce³⁺ and LiLuF₄:Ce³⁺. For LuF₃:Ce³⁺ crystal no fine structure was detected in the spectra even at the highest spectral resolution. Under the host excitation, the fine structure for high-energy emission band of Ce³⁺ (5d-²F_5/2) in LiLuF₄:Ce³⁺ becomes well pronounced because of weaker reabsorption effect, as compared to Ce³⁺ 4f-5d absorption, due to small penetration depth for exciting radiation. As a result the crystal-field splitting for ²F_7/2 and ²F_5/2 levels of Ce³⁺ in LiLuF₄ crystal was measured. First observation of zero-phonon lines at ∼81,550 and ∼82,900 cm⁻¹ as well as vibronic side bands due to interconfigurational 4f¹⁴-4f¹³5d transitions in Lu³⁺ is reported for excitation spectrum of LiLuF₄:Ce³⁺.     

Low temperature electrical conductivity,dielectric constant,and phase transitions in (NH4)2SO4 and (ND4)2SO4

Careful axiswise measurements of d.c. conductivity and dielectric constants of (NH₄)₂SO₄ from 50 to - 196°C establish two distinct phase transitions, instead of one, at temperatures -49.5 and -58°C which remain unchanged in (ND₄)₂SO₄. Explanation based on successive distortions of non-equivalent (NH₄)⁺ is offered. Low temperature transport process in the crystal also is discussed.     

V4+ in SrTiO3: A Jahn-Teller impurity

EPR results of V⁴⁺, with $\text{S =}\text{1}\text{2}$, in SrTiO₃ are reported. The tetragonal local symmetry of the impurity ion is related to strong T_2g × ?_g coupling as evidenced by intensity variations in the presence of stress. At 4.2 K the V⁴⁺ EPR behaviour is related to the intrinsic local strain in SrTiO₃.     

Vibrational modes in ZnAl2S4 and CdIn2S4 crystals

Infrared reflectivity spectra and Raman scattering of the ZnAl₂S₄ and CdIn₂S₄ crystals have been investigated. Reflectivity spectra contours were calculated and phonon parameters and dielectric constants were determined. Effective charges for the Zn, Cd, In and S ions of these materials were determined.     

X-ray diffraction measurement of the Jahn-Teller distortion in TmVO4

Single crystal X-ray diffraction has been used to determine the magnitude and temperature dependence of the tetragonal-to-orthorhombic distortion below the cooperative Jahn-Teller phase transition occuring in TmVO₄ at 2.15 K. The results are in good agreement with mean field theory and with the results of a previous investigation of the soft acoustic mode above the transition. It can be concluded that the interaction of long wavelength acoustic phonons with the ground doublet of the Tm³⁺ ion is the dominant mechanism for the transition.     

Ferroelectric phase transitions in NH4HSeO4 crystals

Results are presented of measurements of spontaneous polarization, electric permittivity and electrical conductance of NH₄HSeO₄ crystals in three principal crystallographic directions from liquid nitrogen temperature to 320 K. NH₄HSeO₄ crystals exhibit ferroelectric properties in the a-axis direction between 106–250 K, whereas in the b-direction they are pyroelectrie over the entire temperature range. The calculated activation energy (1.42 eV) is indicative of semiconducting behavior.     

Magnetization and magnetic susceptibility of single crystals of HoTiO3 and ErTiO3

Bulk magnetization measurements have been performed on single crystals of HoTiO₃ and ErTiO₃. The easy direction of magnetization is along the b-axis for HoTiO₃ and along the c-axis for ErTiO₃ with respect to the Pbnm chemical cell. These findings are in qualitative agreement with the results of two independent powder neutron diffraction studies. The saturation magnetic moments at 4.2 K along the easy axes are 7.3(2)μ_B per formula unit for HoTiO₃ and 6.9(2)μ_B for ErTiO₃. In addition, single crystal susceptibility data were analyzed using the theory of Boutron to yield values for the Heisenberg exchange coupling and the second-order crystal field terms B⁰₂ and B²₂.     

Birefringence of CuGa2S4 crystals

The interference of optical transmission spectra of thin CuGaS₂ single crystals is measured in E||c and E⊥c polarizations. The spectral dependencies of the refractive indexes n_o, n_e and Δn = n_o − n_e near the absorption edge have been determined from interference spectra. The intersection of refractive indexes at two wavelengths has been revealed at 300 K and 10 K. The characteristics of Band-Pass-Mode Filter and Band-Elimination-Mode Filter have been measured, which possess 7 narrow absorption (transmission) bands and represent a comb filter. The characteristics of these filters have been studied.     

Fabrication and magnetic response probed by RF transverse susceptibility in La0.67Ca0.33MnO3 nanowires

The temperature and magnetic field dependence of the radio-frequency (RF) transverse susceptibility (χ_T) of La_0.67Ca_0.33MnO₃ crystalline nanowires has been studied using a very sensitive self-resonant tunnel-diode oscillator (TDO) technique. The nanowires were synthesized using porous templates of anodized alumina by chemical solution deposition technique, and the crystalline nature of the nanowires with the average diameter of 70 nm was confirmed by TEM, SAED, and HREM. RF transverse susceptibility experiments reveal the presence of a double-peak structure at T≤245 K (the Curie temperature) but a single peak at T>245 K. This distinguishes the low temperature ferromagnetic state from the high temperature paramagnetic state. The effective magnetic anisotropy field (H_K), which corresponds to the peak location of χ_T, has been found to increase with decrease in temperature from the Curie temperature.     

Magnetic structure and collective Jahn-Teller distortions in nanostructured particles of CuFe2O4

The aim of the present work is to compare the structural, the composition and chemical state of the surface and magnetic properties of different nanosized CuFe₂O₄ powders exhibiting collective Jahn-Teller effect. The samples under examination consist of edged nanosized particles (needle like) with average length 1300 ± 20 nm and diameter 300 ± 20 nm obtained after high temperature synthesis, and superparamagnetic (at room temperature) spherical particles (d = 6 ± 2 nm), obtained by soft chemistry techniques. The surface composition of the particles was investigated by X-ray photoelectron spectroscopy (XPS). Mössbauer spectroscopy (MöS), including at high magnetic field up to 5 T and 4.2 K, was used for characterization of cation distribution in the samples. The data yielded by the XPS and MöS analyses for spherical nanosized particles led us to the assumption for the existence of a Jahn-Teller effect gradient—from the B-sublattice on the surface to a compensation of the tetragonal distortion in the two sublattices in the core. The analysis of the contribution of the anisotropy energy in edged and spherical nanoparticles shows that it must be considered as an effective value reflecting the influence of the individual factors depending on the particle shape and surface.