Electric-field effect in a mixed-valence ion pair Cr3+−Cr2+ in a KZnF3 crystal

The influence of an external axial electric field on the absorption spectrum of a Cr³⁺−Cr²⁺ mixed-valence pair center coupled by the double-exchange mechanism in a KZnF₃ crystal is investigated. It is shown experimentally that the Cr³⁺−Cr²⁺ pair has an electric dipole moment. The migration of an electron is accompanied by local lattice strain. At the minima of the adiabatic potential, the intermediate fluorine atom is displaced from the lattice site. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 2, 147–149 (25 July 1998)     

Anomalous magnetic properties of ferrites of the CuFe2−x CrxO4 system with high Cr3+ content

The paper reports on a comprehensive study of magnetic properties of CuFe_2−x Cr_xO₄ ferrites (x=0.0, 0.2, 0.3, 1.0, 1.4, 1.6, and 2.0). The curves of magnetization versus temperature, σ _s(T), of the ferrites with x=1.0, 1.4, and 1.6 have anomalous shapes: the magnetization begins to fall off at lower temperatures than the Curie point TC. The experimental results and analysis of exchange interactions suggest that in ferrites with high Cr³⁺ content, magnetic transitions to either a frustrated magnetic structure or a clustered spin glass can take place. Zh. éksp. Teor. Fiz. 111, 1732–1737 (May 1997)     

Effect of external electric field on R line absorption spectra in LiNbO3:Cr3+ crystals

The effect of an external electric field on the R absorption lines of LiNbO₃:Cr³⁺ crystals has been studied by a high-sensitivity differential technique at 77 K. Linear Stark effect has been observed in a field directed along the trigonal crystal axis. No effect of the field was observed when directed perpendicular to this axis. These characteristics of the Stark effect provide a convincing argument for the electric dipole moments of Cr³⁺ centers being oriented along the trigonal C ₃ axis of the crystal and indicate that the chromium centers in LiNbO₃ have C ₃ symmetry. Fiz. Tverd. Tela (St. Petersburg) 39, 2053–2056 (November 1997)     

Optical characterization of Cr3+ centers in LiNbO3

Low-temperature luminescence spectra of stoichiometric Cr:LiNbO₃, congruent Cr:LiNbO₃ and congruent Cr,Mg:LiNbO₃ were studied. Dominant low-field and minor high-crystal-field optical centers are the Cr³⁺ impurity ions that preferentially occupy Li⁺ sites (Cr_Li) in the Cr:LiNbO₃ crystals. Low-field centers related to Cr³⁺ substitution of Nb⁵⁺ (Cr_Nb) occur in addition to Cr_Li in co-doped Cr,Mg:LiNbO₃ samples. Application of high hydrostatic pressure leads to the transformation of dominant Cr³⁺ centers from low- to high-field type due to strong pressure-induced blue shift of the ⁴ T ₂ state, resulting in its crossing with the ² E state of Cr³⁺. This level-crossing effect was observed for the dominant Cr³⁺ _Li and Cr³⁺ _Nb centers at pressures that correlate well with estimations based on the ⁴ T ₂-² Eenergy gap (230 cm^-1 and 1160 cm^-1) and on the rate of their pressure-induced change (14.35 and 11.4 cm^-1/kbar, respectively). We also studied inhomogeneous broadeningof the ² E?⁴ A ₂transitions at ambient pressure for the minor high-field “defect” Cr³⁺ _Li centers in congruent LiNbO₃. A fine structure in the spectral response of these centers was observed. The obtained results are discussed on the basis of a microscopic hierarchic model for perturbed Cr³⁺ ions in the LiNbO₃ lattice. Received: 25 June 2001 / Published online: 2 November 2001     

Investigation of local lattice structure around Cr3+ ions at the trigonal and tetragonal sites in RbCdF3: Cr3+ crystal

The local lattice structure and EPR, optical spectra for Cr³⁺ doped in RbCdF₃ crystal have been studied by diagonalizing the complete energy matrices. The results show that the local structure of the Cr³⁺ ions in RbCdF₃ exhibits a compressed distortion at the trigonal and tetragonal sites. The compressed distortion can be ascribed to the fact that the radius of Cr³⁺ ion is smaller than that of Cd²⁺ ion, and therefore Cr³⁺ ion will draw the fluorin ligands inwards. The variational ranges of the local structural parameters for Cr³⁺ doped in RbCdF₃ crystal R =?1.9491 Å ～?1.9814 Å, θ?= 55.234° ～?55.286° at the trigonal site and R ₁ =?1.8617 Å ～?1.8928 Å, R ₂ =?1.9527 Å ～?1.9851 Å at tetragonal site are obtained respectively, and the EPR and optical spectra agree well with the experimental results.     

Anisotropy of nonlinear absorption in Co<Superscript>2+</Superscript>:MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> crystal

Anisotropy of the nonlinear absorption of Co²⁺ ions in MgAl₂O₄ single crystal at the wavelengths of 1.35 and 1.54 μm has been experimentally demonstrated. The experimental data are analyzed in the framework of a phenomenological model when the Co²⁺ ions are described as three sets of linear dipoles oriented along the crystallographic axes. Ground-state and excited state absorption cross-sections at 1.35 and 1.54 μm are evaluated to be σ_gsa=(4.0±0.3)×10^-19, σ_esa=(3.6±0.4)×10^-20 cm² and σ_gsa=(5.1±0.3)×10^-19, σ_esa=(4.6±0.4)×10^-20 cm², respectively. PACS 42.55.Rz; 71.20.Be     

EPR of the ferroelectric phase transition in Li2Ge7O15:Cr3+ crystals

A Cr³⁺ EPR study of lithium heptagermanate crystals, Li₂Ge₇O₁₅ (LHG), close to the phase transition is reported. Orientation dependences of the spectra in the paraelectric phase of LHG have been measured. An anomalous broadening of the resonant lines accompanied by a crossover in their shape was found in the vicinity of the transition point. Doublet splitting of the EPR lines was observed to occur below T _C as a result of emergence of two structurally nonequivalent positions for Cr³⁺ ions. Fiz. Tverd. Tela (St. Petersburg) 40, 1102–1105 (June 1998)     

Absorption and EPR spectra of Cr3+ ions in a LaBeAl11O19 crystal

Electron spectra of optical absorption and EPR of Cr³⁺ ions in a LaBeAl₁₁O₁₉ crystal are investigated. It is shown that the Cr³⁺ ions occupy, three different octahedral positions of Al³⁺ in the LaBeAl₁₁O₁₉ structure, namely, 12k, 2a, and 4f₂; the ratio of their intensitites is 1∶2∶30, respectively. Parameters of the Cr³⁺ centers are determined and its is shown that the optical absorption spectra in the visible region are practically determined by the Cr³⁺ (III) occupying the 4f₂-positions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 2, pp. 275–277, March–April, 1999.     

Magnetoresistance of the semiconducting spinelide Cu0.625Ga0.375Cr2Se4 having a low-temperature long-range magnetic order-spin glass transition

A study is reported of the dependence of magnetoresistance Δρ/ρ on the square of magnetization σ ² of the semiconducting spinelide Cu_0.625Ga_0.375Cr₂Se₄, which exhibits a low-temperature transition from long-range magnetic order (LRMO) to the spin glass (SG) state in strong magnetic fields. It is shown that at the freezing temperature T _f the Δρ/ρ(σ ²) relations change their slope, and that below T _f this slope is about one half that for T>T f. This finding, together with the earlier observation that the freezing temperature does not depend on the frequency of the ac magnetic field in which it was measured, suggests that the spin-glass phase consists of spins of individual Cr³⁺ ions, and that the SG-LRMO crossover is a phase transition. Fiz. Tverd. Tela (St. Petersburg) 40, 315–317 (February 1998)     

EPR and dielectric relaxation of Fe3+ in KTaO3

EPR and the method of dielectric losses have been used to investigate Fe³⁺ centers of axial and orthorhombic symmetry in KTaO₃ single crystals. The EPR spectrum of orthorhombic-symmetry Fe³⁺ obtained in the 8-mm wavelength range at T=77 K is described by the spin-Hamiltonian with parameters g _x=1.98, g _y=2.01, g _z=2.00, D=0.43 cm⁻¹, and E=5.87×10^t-2 cm⁻¹. From the dielectric measurement data we have obtained the following parameters of the relaxation of the orthorhombic Fe³⁺ centers in KTaO₃: characteristic relaxation frequency τ ₀ ⁻¹ =2.33×10¹² Hz and activation energy E _a=0.044 eV. A model of the orthorhombic Fe³⁺ center in KTaO₃ is discussed within the framework of the kinetic parameters obtained. Fiz. Tverd. Tela (St. Petersburg) 39, 861–864 (May 1997)     

Symmetries and causes of the coincidence of the emission spectra of mirrors and charges in 1+1 and 3+1 spaces

This paper discusses the symmetry of the wave field that lies to the right and left of a two-sided accelerated mirror in 1+1 space and satisfies a single condition on it. The symmetry is embodied in the Bogolyubov matrix coefficients α and β that connect the two complete sets of solutions of the wave equations. The amplitudes of the quantum processes in the right and left half-spaces are expressed in terms of α and β and are related to each other by the transformation (12). The coefficient β _ω′ω ^* plays the role of the source amplitude of a pair of oppositely directed particles with frequencies ω and ω′ of which one is in the left half-space and the other is in the right half-space because one of them has undergone reflection. Such an interpretation makes β _ω′ω ^* observable and explains why, as shown by Eq. (1) and found earlier by Nikishov and Ritus [Zh. éksp. Teor. Fiz. 108, 1121 (1995); transl. JETP 81, 615 (1995)] and by Ritus [Zh. éksp. Teor. Fiz. 110, 526 (1996); transl. JETP 83, 282 (1996)], the emission spectra of a mirror in 1+1 space coincide with those of charges in 3+1 space. The reason is that the angular momentum of the pair emitted by the mirror coincides with the angular momentum of the single particle emitted by the charge. Zh. éksp. Teor. Fiz. 114, 46–62 (July 1998)     

High-frequency tunable EPR spectroscopy of Cr3+ in synthetic forsterite

The electron paramagnetic resonance spectra of isolated and dimer impurity centers of trivalent chromium ions in the octahedral Ml sites in synthetic forsterite are studied in the frequency range of 65–90 GHz. The measurements are performed at 4.2 K in magnetic field from ?0.04 to 0.3 T. The zero-field splitting between spin doublets of the isolated Cr³⁺ ion Δ_s = 66.7 GHz and between spin sublevels of the Cr³⁺-Cr³⁺ dimer Δ_d1 = 71.5 GHz and Δ_d2 = 73.0 GHz is measured directly at zero field. The analysis of the spin Hamiltonian parameters shows that the dimer center consists of a pair of Cr³⁺ ions with an Mg²⁺ vacancy between them replacing three Mg²⁺ ions situated in a quasi-one-dimensional chain aligned parallel to the crystal c-axis. It is found that the exchange interaction in the dimer is ferromagnetic with parameters J_z = 0.47 GHz and J_t = 0.79 GHz.     

Critical point phenomena in the electrical resistivity of binary liquid systems: CS2 + CH3CN and CS2 + CH3NO2

Electrical resistance measurements are reported on the binary liquid mixtures CS₂ + CH₃CN and CS₂ + CH₃NO₂ with special reference to the critical region. Impurity conduction seems to be the dominant mechanism for charge transport. For the liquid mixture filled at the critical composition, the resistance of the system aboveT _c follows the relationR=R _c−A(T−T _c) ^b withb=0·6±0·1. BelowT _c the conductivities of the two phases obey a relation σ₂−σ₁=B(T _c−T)^β with β=0·34±0·02, the exponent of the transport coefficient being the same as the exponent of the order parameter, an equilibrium property.     

Influence of the reagent vibration on the stereo-dynamics of the reactions D- + H2 and H- + D2

Employing the quasi-classical trajectory method and the potential energy surface of Panda and Sathyamurhy [Panda A N and Sathyamurthy N 2004 J. Chem. Phys. 121 9343], the effect of the reagent vibration on vector correlation of the ion-molecule reactions D^- + H₂ and H^- + D₂ is studied at a collision energy of 35.7 kcal/mol. Four generalized polarization-dependent differential cross sections (2π/σ)(dσ₀₀/dω_t),(2π/σ)(dσ₂₀/dω_t),(2π/σ)(dσ₂₂/dω_t), and (2π/σ)(dσ₂₀/dω_t) are presented in the centre-of-mass reference frame, separately. At the same time, the effects on the product angular distributions P(θ_r), P(φ_r) and P(θ_r,φ_r) of the title reactions are also analysed. The calculated results show that the scattering tendencies of the product HD, the alignment and the orientation of j' sensitively depend on reagent molecule vibration.     

Growth,spectroscopic and laser properties of Yb<Superscript>3<Emphasis Type="Bold">+</Emphasis></Superscript>-doped GdAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> crystal: a candidate for infrared laser crystal

Yb³⁺:GdAl₃(BO₃)₄ (hereafter Yb³⁺:GAB) crystals with large sizes and good optical quality have been grown by the top-seed solution growth (TSSG) method. The polarized absorption and emission spectra have been investigated at room temperature. For the σ-polarization, the intensities of both absorption and emission spectra are stronger than those for the π-polarization, the σ-absorption cross section of Yb³⁺ in GAB being 3.43×10^-20 cm² at 977 nm, and the σ-emission cross section being 0.98×10^-20 cm² at 1045 nm. The fluorescence lifetime of the ² F _5/2→² F _7/2 transition was measured to be 800 μs in the 5% doped sample used for our laser experiments, 993 μs in a 10% doped sample and 569 μs in a 0.5% doped sample. The laser parameters were estimated as: β_min=0.022, I_sat=10.4 kW/cm² and I_min=0.23 kW/cm². About 0.4 W laseroutput at the wavelength of 1043 nm was achieved when the Yb³⁺:GAB crystal was pumped by a 974 nm laser diode, with 27.4% slope efficiency. PACS 42.55.-f; 42.70.Hj; 78.20.-e; 81.10.Dn     

Study of spectroscopic characteristics of holmium-doped double sodium-yttrium fluoride crystals Na<Subscript>0.4</Subscript>Y<Subscript>0.6</Subscript>F<Subscript>2.2</Subscript>:Ho<Superscript>3+</Superscript>

We have grown crystals Na_0.4Y_0.6F_2.2:Ho³⁺ (NYF:Ho³⁺) by the Bridgman-Stockbarger method. The optical spectra and luminescence kinetics of NYF:Ho³⁺ crystals have been studied. Based on the analysis of low-temperature absorption spectra, we determine the structure of the Stark splitting of holmium levels in NYF:Ho³⁺ crystals. From absorption spectra examined at T = 300 K, we calculate absorption cross-section spectra and oscillator strengths of transitions from the ground state of holmium to excited multiplets. We show that the absorption spectra of NYF:Ho³⁺ crystals consist of broad bands that lie in the UV, visible, and near-IR ranges. The most intense bands are observed in the visible range, they correspond to transitions ⁵ I ₈ → (⁵ F ₁, ⁵ G ₆) and ⁵ I ₈ → (⁵ F ₄, ⁵ S ₂), and their maximal absorption cross sections are σ_abs^max (λ = 450.3 nm) = 1.16 × 10⁻²⁰ cm² and σ_abs^max (λ = 535.1 nm) = 0.9 × 10⁻²⁰ cm². The intensity parameters Ω _t have been calculated by the Judd-Ofelt method taking into account 10, 12, and 20 transitions from the ⁵ I ₈ ground state to excited multiplets. We show that, with an increasing number of transitions taken into account in the calculation, the parameters Ω _t somewhat increase. For 20 transitions, we have obtained the following intensity parameters: Ω₂ = 0.97 × 10⁻²⁰, Ω₄ = 1.74 × 10⁻²⁰, and Ω₆ = 1.15 × 10⁻²⁰ cm². With these parameters, we have calculated the probabilities of radiative transitions, the radiative lifetimes, and the branching ratios. The rates of multiphoton nonradiative transitions have been estimated. The luminescence decay kinetics from excited holmium levels ⁵ F ₃ (⁵ F ₄, ⁵ S ₂) and ⁵ F ₅ have been studied upon selective excitation in the range of 490 nm, and the lifetimes of these levels have been experimentally determined. We find that the calculated and experimental rates of radiative and nonradiative relaxation from excited holmium levels agree well with each other. We show that, upon pumping in the range of 490 nm, the multiplet (⁵ F ₄, ⁵ S ₂) is populated as a result of the radiative and nonradiative excitation relaxation from the ⁵ F ₃ level, while the lower-lying ⁵ F ₅ level is populated due to direct radiative transitions ⁵ F _{3, 2} → ⁵ F ₅, obviating the cascade scheme ⁵ F ₃ → (⁵ F ₄, ⁵ S ₂) ↝ ⁵ F ₅. We conclude that NYF:Ho³⁺ crystals are processable; admit doping by holmium in high concentrations (up to 100%); and, with respect to all their radiative characteristics, can be considered as potential active media for solid-state continuously tunable lasers in the IR and visible ranges.     

New data for the 197Au(γ, nX) and 197Au(γ, 2nX) reaction cross sections

The results from experimental and theoretical studies of the total and partial cross sections of photoneutron reactions on the ¹⁹⁷Au isotope were analyzed. The cross sections for reactions σ(γ, nX) = σ(γ, n) + σ(γ, np) + … + σ(γ, 2nX) = σ(γ, 2n) + σ(γ, 2np) + … were evaluated in the energy range 7 ≤ E _γ ≤ 30 MeV using an approach free of the shortcomings of experimental photoneutron multiplicity sorting methods. The total photoneutron reaction cross sections σ^exp(γ, xn) = σ^exp(γ, nX) + 2σ^exp(γ, 2nX) + … = σ^exp(γ, n) + σ^exp(γ, np) + 2σ^exp(γ, 2n) + 2σ^exp(γ, 2np) + … were used as the initial experimental data. The contributions from the cross sections σ(γ, nX) and σ(γ, 2nX) to the cross sections σ^exp(γ, xn) were separated using the multiplicity transition functions F ₁ ^theor = σ^theor(γ, 1nX)/σ^theor(γ, xn) and F ₂ ^theor = σ^theor(γ, 2nX)/σ^theor(γ, xn), calculated within an updated version of the pre-equilibrium model of photonuclear reactions. New evaluated data for both partial reaction cross sections, i.e., σ^eval (γ, 1nX) = F ₁ ^theorσ^exp(γ, xn) and σ^eval(γ, 2nX) = F ₂ ^theorσ^exp(γ, xn), were obtained. The cross sections σeval(γ, nX) and σ^eval.(γ, 2nX) evaluated using the theoretically calculated functions F _1,2^theor are consistent with the Livermore data, but substantially contradict the Saclay data.     

Influence of samarium on optical absorption in thin films of the solid electrolyte RbAg4I5

The fundamental optical absorption of films of the solid electrolyte RbAg₄I₅ electrolyte films decreases (by approximately 25%) after vacuum evaporation of Sm films onto them, and a broad strong-absorption band with a maximum at 2.4 eV appears within the bad gap. The films bleach after 5–10 days in dry air. The observed phenomena are attributed to a high concentration (∼3×10²⁰ cm⁻³) of point defects, including F-centers, in nonstoichiometric RbAg₄I₅:Sm, and also to the oxidation of Sm. In colored films the ionic conductivity is σ⋍0.9σ ₀, and in bleached films it is close to the initial value σ ₀. Fiz. Tverd. Tela (St. Petersburg) 39, 1544–1547 (September 1997)     

Spectroscopic and laser properties of Cr3+:Yb3+:Er3+: fluoride phosphate glass

Sensitization of the fluorescence of Er³⁺ in fluoride phosphate glass containing up to 20 mol% phosphates by codoping with Cr³⁺ and Yb³⁺ is shown. The low order of ligand field strength for Cr³⁺ (Dq/B=2.04) results in broad Cr³⁺ fluorescence overlapping the Yb³⁺ absorption. The electronic energy transfer efficiency approaches 100%. Deviations of donor decay from the Förster law are interpreted in terms of the inhomogeneously acceptor distribution. The electronic energy transfer efficiency of Yb³⁺ → Er³⁺ reaches a maximum value of 75% for glasses containing 20 mol% phosphates. The transfer is shown to be migrationally accelerated by means of GAF-LAF-FB theory. From Judd-Ofelt parameters a stimulated emission cross-section for the transition⁴I_13/2 →⁴I_15/2 of Er³⁺ of 6.2×10⁻²⁰ cm² is derived. The c.w. laser action of Er³⁺ by Cr³⁺ excitation and double-step energy transfer is shown. The output is tuned continuously from 1536 to 1596 nm. Flashlamp pumping is also shown.