Magnetization behaviour of DyAl2 single crystals

We report the theoretical interpretation of the magnetization and the magnetocrystalline anisotropy of ferromagnetic DyAl₂ single crystals between 4.2 and 60 K and magnetic fields up to 15 T. Good agreement between theory and experiment is obtained by using three temperature independent parameters: the two crystal field parameters B₄ = (?0.50 ± 0.05) × 10^?4 meV, B₆ = ? (0.51 ± 0.05) × 10^?6 meV and the Curie temperature T_c = (62 ± 2) K.     

EPR study of Fe3+ and Mn2+ in CeO2 and ThO2

Attempts were made to grow CeO₂ and ThO₂ single crystals doped with transition metal ions. Only Fe³⁺ and Mn²⁺ could be detected by the EPR technique. The EPR spectrum of Fe³⁺ in CeO₂ exhibits the well-known fine structure in cubic fields. The parameters areg=2.0044(1) anda=15.6(1)·10^?4 cm^?1. The hyperfine constantA for⁵⁷Fe in hexahedral coordination was found to be 8.9(1)·10^?4 cm^?1. The EPR spectrum of Mn²⁺ in CeO₂ reveals two cubic Mn²⁺ centers. The parameters for center 1 areg=1.9999(1) andA=86.9(1)·10^?4 cm^?1 and for center 2g=1.9984(1) andA=87.0(1)·10^?4 cm^?1. Heating the Mn doped CeO₂ samples in hydrogen, the Mn²⁺ centers transform from cubic into trigonal centers with approximate values ofg=1.9988(2),A=84.5(6)·10^?4 cm^?1 andD=203(1)·10^?4 cm^?1. The two observed Mn²⁺ centers in ThO₂ exhibita priori axial symmetry with approximate values ofg=2.0006(2),A=88.9(4)·10^?4 cm^?1 andD=33(3)·10^?4 cm^?1.     

Ferroelectric and optical properties of Ba6Ti2Nb8O30 single crystals

The dielectric, optical and non-linear optical properties of Ba₆Ti₂Nb₈O₃₀ single crystals were examined from room temperature up to the Curie temperature of 245°C. The spontaneous polarization at room temperature was estimated as 0·22±0·01 C/m². The linear electrooptic constants were measured as r₃₃^T=(1·17±0·02)×10^?10 and r₁₃^T=(0·42±0·01)×10^?10 m/V. The non-linear optical coefficients were d₃₃=(15·1±2·0)×10^?12 and d₃₁=(11·0±2·0)×10^?12 m/V, which are comparable to those of Ba₄Na₂Nb₁₀O₃₀. Temperature dependences of δ₃₃ and δ₃₁ (Miller's δ) were found to be proportional to that of P_s.     

Crystal field parameters and phase transitions in ErSb

The crystal field levels of the Er ($\text{J =}\text{15}\text{2}$) ion in a single crystal of ErSb have been measured by inelastic neutron scattering. The crystal field parameters obtained by a least squares fit to the spectra at several temperatures are: B₄ = (0·473 ± 0·005) × 10^?2°K and B₆ = (0·59 ± 0·06) × 10^?5°K, which differ considerably from the values o by interpolation from measurements on other compounds. In addition the temperature dependence of the magnetic scattering in the vicinity of the Néel temperature (T_N = 3·55°K) clearly demonstrates that the transition is second order in contrast to the first order behavior suggested by specific heat measurements. Also, any lattice distortion accompanying the magnetic ordering is less than 0.1 per cent, the resolution of the present experiment.     

Temperature dependence of Mn2+ EPR in Sn2P2S6 near the phase transition

The X-band EPR spectrum of Mn²⁺ in Sn₂P₂S₆ was studied in the temperature rangeT=223–363 K. At room temperature the spin-Hamiltonian constants areg=2.00±0.01,B ₂ ⁰ =(163±3)·10^?4 cm^?1,B ₂ ² =(159±3)·10^?4 cm^?1,A=?(75±1)·10^?4 cm^?1. The effect of the invariance in temperature of the resonance magnetic fields in the narrow temperature rangeT=337–340 K and the model of the paramagnetic centre are discussed. According to EPR data a phase transition occurs atT=337 K. This transition from the paraelectric phase to the ferroelectric one is accompanied by a dramatic change in value of the spin-Hamiltonian constantB ₂ ⁰ .     

Iodine as a donor in CdS

Iodine doped single crystals of CdS were grown from the vapor phase. High temperature Hall effect measurements for the crystals equilibrated with Cd and S₂ vapors at temperatures between 700 and 1000°C gave the free electron concentration as a function of p_Cd or p_S2 and temperature. The results can be explained on the basis of a model in which the CdS is saturated with iodine at low p_Cd (=high p_S2) but unsaturated at high p_Cd.The solubility of iodine in CdS is given by c_t=1·73×10²²p_S2^?1/8 exp (?1·045 eV/kT) cm^?3 atm^?1/8=4·62×10¹⁹p_Cd^1/4 exp (?0·195 eV/kT) cm^?3 atm^1/4The formation of pairs (I_SV_Cd)′ from I_S^· and V_Cd″ is governed by the equilibrium constant K_{P(I, V)}=4 exp (≤1·1 eV/kT)If Cd diffusion occurs primarily by free vacancies, the Cd^* tracer self diffusion leads to a vacancy mobility of (1·2±0·5)×10^?5 cm² sec^?1 at 900°C, in agreement with results reported by Woodbury [12], but (7±3) times larger than reported by Kumar and Kroger [10].     

Die Temperaturabhängigkeit des Bandabstandes von Bleiselenid,gemessen an photoleitenden Schichten

The temperature dependence of spectral distribution of photoconductivity was measured on evaporated polycrystalline layers of lead-selenide in the range from 80 to 300 °K. The method ofBardeen, Blatt andHall was used, to calculate the band gap for direct and indirect transitions. A linear positive temperature coefficient was obtained for both transitions. The values areβ _dir=+(4.5±0.2) · 10^?4 eV/°K andβ _ind=+(3.0±0.2)· 10^?4eV/°K.     

EPR study of the ferroelectric phase transition in chromium-doped DMAAS

X-band electron paramagnetic resonance (EPR) investigations of single crystals of Cr³⁺-doped dimethylammonium aluminium sulphate hexahydrate are presented from 100 K to room temperature. The crystal undergoes a phase transition at 152 K from the ferroelastic to the ferroelectric phase. The spin-Hamiltonian parameters have been determined for both phases. The spin-Hamiltonian parameters in the ferroelectric phase are:g=1.980±0.003,b ₂ ⁰ =(1140±15)·10^?4 cm^?1,b ₂ ² =(214±10)·10^?4 cm^?1. Remarkable EPR line width changes confirm the order-disorder character of the ferroelectric phase transition on a microscopic level and demonstrate that the dimethylammonium reorientation freezing-out is the prime reason for this transition.     

Effect of the ionic radius on jump frequencies of alkaline earth cations in NaCl crystals

By comparing diffusion coefficientsD of bivalent cations Ba²⁺, Ca²⁺, Sr²⁺ in NaCl crystals it was shown that in the temperature range above 550 °CD (Ba²⁺)>D (Sr²⁺)>D (Ca²⁺) is valid. Temperature dependences of jump frequenciesw ₂ of these cations are described byw ₂ (Ba²⁺)=(2·15±0·55) × 10¹² × exp {?(0·817±0.007)/kT};w ₂ (Sr²⁺)=(2·9±1·1) × 10¹² × exp {?(0·84±0.02)/kT} andw ₂ (Ca²⁺)=(5·5±6·5) × 10¹⁰ × exp {?(0·51±0·07)/kT}. It was demonstrated that in NaCl crystals the activation enthalpy and the preexponential factor of the jump frequencyw ₂ increase with increasing ionic radius and mass of the bivalent alkaline earth cation.     

Crystal field splitting of Pr3+ in PrAl2 investigated by inelastic neutron scattering

We report the.results of an experimental determination of the crystal field splitting of Pr³⁺ in PrAl₂ by means of inelastic neutron scattering. For the crystal field parameters we obtain B₄ = (47.2 ± 4.0) × 10^?4 meV and B₆ = ? (156 ± 12) × 10^?6 meV.     

Chromium tracer diffusion in NiO crystals

Diffusion of ⁵¹Cr in NiO single crystals in air has been studied by the tracer-sectioning technique. In the temperature range 1192–1642°C, the diffusion coefficient can be expressed by the Arrhenius expression D=D_oexp(-Q/RT), with D_o=(8·6±1·2)×10^?3 cm²/sec and Q=67·4±1·1 kcal/mole. The use of a high specific-activity tracer and a special configuration for the diffusion anneal prevented the self-dopling effect found by Seltzer and the evaporation of chromium from the sample surface. The present results, in conjunction with published results on nickel self-diffusion in NiO and interdiffusion in the NiO?Cr₂O₃ system, are used to determine a chromium ion-vacancy binding energy of about 5 kcal/mole in pure NiO.     

Zeitliches Abklingen und Anisotropie von p-Terphenyl- undp-Terphenyl-Anthrazen-Mischkristallen bei Beschuß mit α-Teilchen

The time dependence of scintillation intensity from single crystals ofp-terphenyl and mixed crystals ofp-terphenyl and anthracene after bombarding with α-particles was investigated at the two temperaturesT=296 °K andT=92 °K. For the crystals ofp-terphenyl the time dependence of the scintillation anisotropy was also measured. Using the formulas given byKing andVoltz the decay curves ofp-terphenyl were decomposed into two components. Good agreement between experiment and theory was found. The ratio of the prompt intensity to the delayed intensity was determined to be 1∶2 atT=296 °K and 1∶3 atT=92 °K. The diffusion constants for triplet excitons were calculated to beD _T(296 °K)≈10^?5 cm² sec^?1 andD _T(92 °K)≈ 2×10^?6 cm² sec^?1, and the triplet-triplet interaction rate constantsχ _tt(296 °K)≈ 2.5×10^?11 cm³ sec^?1 andχ _tt(92 °K)≈0.5×10^?11 cm³ sec^?1.     

Mössbauer studies of europium and ytterbium hydrides

Mössbauer absorption spectra were obtained for the 21·6 ke V transition of ¹⁵¹Eu in EuH₂ at various temperatures and for the 84·3 keV transition of ¹⁷⁰Yb in YbH₂ at 4·1°K. The isomer shift of EuH₂ relative to Eu³⁺: Sm₂O₃ is ? 12·1 ± 0·3 mm. sec^?1, and the magnetic hyperfine field equals ? 305 ± 5 kOe at saturation. The Curie temperature is found to be 16·2 ± 0·05°K, and the critical parameters of the transition are D = 1·17 ± 0·02 and β = 0·35 ± 0·01. The magnetic field is perpendicular to the principal axis of the electric field gradient and the values of the quadrupole hyperfine interaction e²qQ₀(3 cos² θ ? 1)/8 is ? 28 ± 4 Mc . sec^?1. A large increase of the resonance area (21%) occurs at the transitio to the ferromagnetic state. The isomer shift of YbH₂ relative to Yb: TmAl₂ is ?0·11 ± 0·01 mm . sec^?1. The value of the quadrupole coupling constant e²qQ_c/4is ? 91·5 ± 2 Mc . sec^?1 and the asymmetry parameter of the electric field gradient equals 0·89 ± 0·05. The data for EuH₂ and YbH₂ is shown to be consistent with the hydridic model for the rare earth hydrides.     

High resolution measurements of the line positions and strengths of the 2ν2 band of H2CO

Spectra of the 2ν₂ band of formaldehyde have been obtained with high resolution (0.035 cm^?1). Measurements were made with path lengths of 8, 16, and 24 m and at sample pressures from 0.1 to 0.3 mm Hg at room temperature (～296°K). From these data, the following constants were determined for the 2ν₂ band in wavenumber units: v₀=3471.718±0.004,A=9.3958±030013,B=1.28100±0.00024,C=1.11662±0.00024, Tbbb=-12.8±0.5×10^-6,Taabb=60±5×10^-6. The line strengths were also obtained from the data. The strengths were analyzed to determine the band strength and the rotational factors. At 296°K, the strength of the 2ν₂ band was found to be 15.5 ± 0.9 cm^?1/(cm·atm).     

Diffusionskonstante und charakteristische Absorption vor der Bandkante von Mn in ZnO-Kristallen

ZnO single crystals were doped with Mn and Co by diffusion. In the temperature range from 1400–1600 K the Mn and Co-diffusion-constants were determined:D _Mn=3.2 · 10^?3 exp (?2.87 eV/kT) cm² sec^?1 andD _Co=1·10exp(?3.98 eV/kT) cm² sec^?1. The Mn doped ZnO crystals show a characteristic colour due to an absorption near the intrinsic absorption edge. The corresponding absorption spectra were measured forE⊥c andE∥c. A discussion of different absorption mechanism shows that a charge-transfer transition is responsible for this absorption.     

Magnetic and ESR studies of Er3+ in lanthanum dihydride LaH2

Er³⁺ electron spin resonance ESR and magnetic susceptibility have been studied in metallic lanthanum dihydride host. The ESR spectrum contains a single asymmetrical line with g-factor g = 6.68 ± 0.05 close to that expected for Γ₇ as ground state. The experimental magnetic susceptibility was interpreted on the base of LLW cubic crystal field Hamiltonian. The best fit of the experimental data has been obtained for the following B₄ and B₆ crystal field parameters: B₄ = ?5.2 × 10^?3 K; B₆ = 3.8 × 10^?5 K which support the anionic-like character hydridic model of hydrogen atoms in this hydride.     

Mößbauereffekt in Eisenstilben und FeCl2·H2O

Using Mößbauer effect measurements in the temperature range between 3 °K and 310 °K the magnetic fields at the nucleus in iron-stilbene, FeCl₂·H₂O and FeCl₃ are determined to beH _T=0=(250±10) kOe, (252±18) kOe and (468±10) kOe; a Néel-temperature ofT _N=(23±1) °K is measured for iron-stilbene. The electric quadrupole splittings atT=0 °K for iron-stilbene and FeCl₂ ·H ₂ O, ΔE=(+2.52±0.02) mm/sec and (+2.50±0.05) mm/sec, yield electric field gradients at the iron nucleus ofq _z=+9.7·10¹⁷ V/cm² and +9.6·10¹⁷ V/cm², whereq _z⊥H; Debyetemperatures of θ=162 °K and 188 °K are obtained. The energy of the excited 3d-electron levels in iron-stilbene is estimated to Δ₁=309 cm^?1 and Δ₂=618cm^?1 as deduced from the temperature dependence ofΔE. In contrast to the suggestion ofEuler andWillstaedt bivalence of the iron in ironstilbene is found; its composition is shown to be 4(FeCl₂ ·H ₂O)·stilbene.     

On the role of crystal water in the conduction of synthetic borates

The dispersion of permittivity and conductivity of crystals containing aqua complexes of different types (γ-HBO₂, Ca₂B₆O₁₁ · H₂O, La[B₅O₈]OH)₂ · 1.5H₂O, and TRB₆O₉(OH)₃(TR-Tb, Tu)) is studied for the first time. The compounds were synthesized under hydrothermal conditions at T = 270–280°C and P = 70–100 atm. Depending on the contained aqua complex, the compounds display different temperature and frequency behavior of the electric properties. The measurements are carried out in the frequency range from 10^?2 to 10⁶ Hz and in the temperature range from ?20 to 140°C.     

EPR, Optical Absorption and Superposition Model Study of Fe3+-Doped Ammonium Dihydrogen Phosphate Single Crystals

X-band electron paramagnetic resonance (EPR) studies are carried out on Fe³⁺ ions doped in ammonium dihydrogen phosphate (ADP) single crystals at room temperature. The crystal field and spin Hamiltonian parameters are evaluated from the resonance lines obtained at different angular rotations. The obtained values of spin Hamiltonian and zero-field parameters of the Fe³⁺ ion in ADP are: g = 1.994 ± 0.002, |D| = (220 ± 5) × 10^?4 cm^?1 and a = (640 ± 5) × 10^?4 cm^?1. On the basis of EPR data, the site symmetry of the Fe³⁺ ion in the crystal is discussed. The Fe³⁺ ion enters the lattice substitutionally replacing the NH₄ ⁺ sites. The optical absorption of the crystal is also studied at room temperature in the wavelength range of 195–925 nm. The energy values of different orbital levels are calculated. The observed bands are assigned as transitions from the ⁶ A _1g (S) ground state to various excited quartet levels of the Fe³⁺ ion in a cubic crystalline field. From the observed band positions, Racah interelectronic repulsion parameters (B and C), cubic crystal field splitting parameter (D _q ) and Trees correction are calculated. There values are: B = 970, C = 1,923, D _q  = 1,380 cm^?1 and α = 90 cm^?1, respectively. On the basis of EPR and optical data, the nature of bonding in the crystal is discussed. The zero-field splitting (ZFS) parameters are also determined theoretically using B _kq parameters estimated from the superposition model. The values of ZFS parameters thus obtained are |D| = (213 ± 5) × 10^?4 cm^?1 and |E| = (21 ± 5) × 10^?4 cm^?1.     

Study of the semi-conducting properties of pyrolusite

The electrical conductivity σ of the specimens is found to obey a relation of the type σ=C exp (?B/k T) over a temperature range 300 to 500° K whereC andB are constants. The experimentally determined values ofB and C are (1)B≈1490 to 2199 (2)C ≈ 0·72 × 10^?3 to 4·9 × 10^?3 ohms^?1 cms^?1. The value of the activation energy determined from the values ofB are ≈0·13 to 0·19 e.V. In A.C measurements σ is found to vary with voltage applied across the specimen at a given temperature. The i?V characteristics of metal point semi-conductor contacts are non-linear symmetrical curves and are strongly temperature dependant. The value of the Hall constant (?0·14 cm³/coul) yields carrier concentration as 4·3 × 10¹⁹/cm³, and mobility 1·2 cm² volt^?1 second^?1. Δ?/? for the specimen is found to vary asH ² where ? is the resistivity andH the value of magnetic field. The specimens develop a thermo-electric power of magnitude 200 μV/K to 500 μV/K which is fairly constant over the temperature range 300 to 800° K. The sign of the thermo-e.m.f. and of the Hall constant indicate that the specimens are “n” type.