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.     

Nuclear spin resonance of <Superscript>53</Superscript>Cr in ferromagnetic CuCr<Subscript>2</Subscript>S<Subscript>4</Subscript>: Sb

The influence of variable valence on NSR spectra of ⁵³Cr nuclei in ferromagnetic CuCr_2?xSb_xS₄ (x = 0, 0.02, 0.07) at T = 77 K is considered. For quadrupole nuclei in locally anisotropic positions, the effects of variable valence result in averaging of not only the resonance frequency but also of the quadrupole and magnetic anisotropy constants. The significant difference between the experimental and calculated values of these constants indicates the important role of the intrinsic electronic contribution to the anisotropy of hyperfine fields of compounds containing Cr⁴⁺ ions. Additional lines caused by intrinsic and induced defects in the structure are observed in the spectra of doped and undoped compounds.     

High-frequency EPR of Cr<Superscript>2+</Superscript> ions in CdGa<Subscript>2</Subscript>S<Subscript>4</Subscript>

High-frequency broad-band (65–240 GHz) EPR is used to study impurity centers of bivalent chromium in a CdGa₂S₄ crystal. It is found that the EPR spectra correspond to tetragonal symmetry. The spin Hamiltonian H = βB · g · S + B ₂ ⁰ O ₂ ⁰ + B ₄ ⁰ O ₄ ⁰ + B ₄ ⁴ O ₄ ⁴ with the parameters B ₂ ⁰ =23659±2 MHz, B ₄ ⁰ =1.9±1 MHz, |B ₄ ⁴ |=54.2±2 MHz, g_‖=1.93±0.02, and g_⊥=1.99±0.02 is used to describe the observed spectra. It is concluded that chromium ions occupy one of the tetrahedrally coordinated cation positions.     

Magnetic order in the structurally disordered helicoidal magnet Cr<Subscript>1/3</Subscript>NbS<Subscript>2</Subscript>: NMR at <Superscript>53</Superscript>Cr nuclei

The Cr_1/3NbS₂ magnet is studied by nuclear magnetic resonance (NMR) at ⁵³Cr nuclei in a zero applied magnetic field. The following two frequency ranges are distinguished in the ⁵³Cr NMR spectrum at T = 4.2 K: ν ₁ = 64–68 MHz and ν ₂ = 49–51 MHz. They can be related to two valence states of chromium ions, namely, Cr⁴⁺ and Cr³⁺. The components of the electric field gradient, the hyperfine fields, and the magnetic moment at chromium atoms are determined. The NMR data demonstrate that the magnetic moments of chromium lie in plane ab and form a magnetic structure consisting of regions with a helicoidal magnetic order and regions where this order is broken.     

Spectroscopy of NaLa(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>: Tm<Superscript>3+</Superscript> and NaGd(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>: Tm<Superscript>3+</Superscript> crystals as advanced laser materials

Single crystals of double sodium-containing lanthanum and gadolinium molybdates doped with Tm³⁺ ions were synthesized by the Czochralski method. The spectroscopic properties of these crystals were investigated from the viewpoint of their use as active media in diode-pumped lasers. The polarized spectra of absorption on the ³ H ₄ and ³ F ₄ levels and the polarized spectra of luminescence due to the ³ F ₄-³ H ₆ laser transition were recorded, and the lifetimes of the ³ H ₄ and ³ F ₄ excited states of the Tm³⁺ ions were determined. The luminescence cross sections were calculated using the Füchtbauer-Ladenburg formula. The simulation of the decay curve of the ³ H ₄ excited state according to the Golubov-Konobeev-Sakun method revealed that, in the crystals under investigation, the interaction between Tm³⁺ ions predominantly occurs through the dipole-dipole mechanism.     

Antisite defects and valence state of vanadium in Na<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

Electron paramagnetic resonance (EPR) studies have been performed with the aim of determining the valence state and local crystal structure of the nearest environment of vanadium ions in the initial, charged, and discharged samples of the cathode material Na_xV₂(PO₄)₃ (1 ≤ x ≤ 3). It has been found that the charged sample (x = 1) is characterized by an intense signal corresponding to V⁴⁺ ions located in a highly distorted octahedral crystal field. An EPR signal with the g-factor close to the g-factor of the V⁴⁺ ion has also been observed in the initial sample (x = 3), where the intensity of the resonance signal is one order of magnitude lower than that in the charged sample. It has been revealed that the resonance signal under consideration is associated with the formation of antisite defects when a part of vanadium ions are located in sites of sodium ions. It has also been found that the intensity of this signal increases after a complete charge–discharge cycle (x = 3).     

Experimental Study and Analysis of Absorption Spectra of Ni<Superscript>2+</Superscript> Ions in Nickel Orthoborate Ni<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>2</Subscript>

The results of studies of the absorption spectra of nickel orthoborate Ni₃(BO₃)₂ in the range of electronic d–d-transitions are reported. The obtained data are analyzed in the framework of the crystal field theory. The Ni²⁺ ions are located in two crystallographically nonequivalent positions 2a and 4f with point symmetry groups C_2h and C₂, respectively, surrounded by six oxygen ions forming deformed octahedra. The absorption spectra exhibit three intense bands corresponding to spin-resolved transitions from the ground state of nickel ion ³A_2g (³F) to the sublevels of the ³T_2g (³F), ³T_1g (³F) and ³T_1g (³P) triplets split by the spinorbit interaction and the rhombic component of the crystal field. At temperatures below 100 K, the spectra exhibit a thin structure, in which phonon-free lines can be distinguished. Comparison of the calculated frequencies of the zero-phonon transitions with the experimental data allows estimating parameters of the crystal field acting on the nickel ions in the 2a- and 4f-positions, as well as the parameters of electrostatic interaction between the 3d electrons and spin-orbit interaction constants.     

Thermal quenching of luminescence of BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> crystals activated with Er<Superscript>3+</Superscript> and Tm<Superscript>3+</Superscript> ions

Thermal quenching of interconfigurational 5d-4f luminescence of Er³⁺ and Tm³⁺ ions in BaY₂F₈ crystals is studied in the temperature range of 330–790 K. The quenching temperatures are ~575 and ~550 K for Er³⁺ and Tm³⁺, respectively. It is shown that quenching of 5d-4f luminescence of Tm³⁺ ions is caused by thermally stimulated ionization of 5d electrons to the conduction band.     

Study of absorption spectra of Er<Superscript>3+</Superscript> in KTaO<Subscript>3</Subscript> crystals

The first results of the study of optical absorption spectra of KTaO₃: Er³⁺ crystals are presented. In the 350–660-nm region, lines are observed deriving from intraconfigurational electronic transitions from the ⁴ I _15/2 ground state to levels of the ⁴ F _9/2, ⁴ S _3/2, ² H _11/2, ⁴ F _7/2, ⁴ F _5/2(⁴ F _3/2), ² G _9/2, and ⁴ G _11/2 excited states of the Er³⁺ ions. A comprehensive study of transitions to the ⁴ F _9/2, ⁴ S _3/2, ² H _11/2, and ⁴ F _7/2 levels at 77 K is carried out. The number of lines observed for the above transitions fits the theoretically possible number for ?-? electronic transitions in Er³⁺ ions in the cubic crystal field. In the case of a differently charged substituted ion, this situation occurs only under nonlocal impurity charge compensation. The energies of the excited state levels for the transitions under study are determined.     

Low-temperature time-resolved VUV luminescence spectroscopy of SrF<Subscript>2</Subscript>: Er<Superscript>3+</Superscript> crystals

Time-resolved excitation and emission spectra of SrF₂: Er³⁺ upon selective excitation with synchrotron radiation in the VUV and ultrasoft x-ray ranges at T = 8 K were studied. The VUV luminescence of SrF₂: Er³⁺ derives from high-energy interconfiguration 4f¹⁰5d-4f¹¹ transitions in the Er³⁺ ion. The VUV emission spectrum revealed, in addition to the 164.5-nm band (millisecond-range kinetics), a band at 146.4 nm (with a decay time of less than 600 ps). The formation of excitation spectra for the f-f and f-d transitions in the Er³⁺ ion is discussed.     

Crystal field of Yb<Superscript>3+</Superscript> tetragonal centers in the YbRh<Subscript>2</Subscript>Si<Subscript>2</Subscript> intermetallic compound

The spectra of electron paramagnetic resonance and inelastic neutron scattering in crystals of the heavy-fermion intermetallic compound YbRh₂Si₂ are interpreted. The phenomenological potentials of the crystal electric field of Yb³⁺ tetragonal centers and the parameter of the Hamiltonian for the spin-orbit interaction of electrons are determined from the experimental energy level schemes. A comparison of the results obtained from experimental data on electron paramagnetic resonance, inelastic neutron scattering, and Mössbauer spectroscopy shows that the most probable ground state of Yb³⁺ ions in the YbRh₂Si₂ crystal is the Kramers doublet Γ _t6 ^? .     

Effect of the Lattice and Spin-Phonon Contributions on the Temperature Behavior of the Ground State Splitting of Gd<Superscript>3+</Superscript> in SrMoO<Subscript>4</Subscript>

The temperature behavior of the EPR spectra of the Gd³⁺ impurity center in single crystals of SrMoO₄ in the temperature range T = 99–375 K is studied. The analysis of the temperature dependences of the spin Hamiltonian b ₂ ⁰ (T) = b₂(F) + b₂(L) and P ₂ ⁰ (T) = P₂(F) + P₂(L) (for Gd¹⁵⁷) describing the EPR spectrum and contributing to the Gd³⁺ ground state splitting ΔE is carried out. In terms of the Newman model, the values of b₂(L) and P₂(L) depending on the thermal expansion of the static lattice are estimated; the b₂(F) and P₂(F) spin-phonon contributions determined by the lattice ion oscillations are separated. The analysis of b ₂ ⁰ (T) and P ₂ ⁰ (T) is evidence of the positive contribution of the spin-phonon interaction; the model of the local oscillations of the impurity cluster with close frequencies ω describes well the temperature behavior of b₂(F) and P₂(F).     

High-resolution spectroscopy of HoFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> crystal: a study of phase transitions

The transmission spectra of HoFe₃(BO₃) multiferroic single crystals are studied by optical Fourier-transform spectroscopy at temperatures of 1.7–423 K in polarized light in the spectral range 500–10 000 cm^–1 with a resolution up to 0.1 cm^–1. A new first-order structural phase transition close to the second-order transition is recorded at T_c = 360 K by the appearance of a new phonon mode at 976 cm^–1. The reasons for considerable differences in T_c for different samples of holmium ferroborate are discussed. By temperature variations in the spectra of the f–f transitions in the Ho³⁺ ion, we studied two magnetic phase transitions, namely, magnetic ordering into an easy-plane structure as a second-order phase transition at T_N = 39 K and spin reorientation from the ab plane to the c axis as a first-order phase transition at T_SR = 4.7 ± 0.2 K. It is shown that erbium impurity in a concentration of 1 at % decreases the spin-reorientation transition temperature to T_SR = 4.0 K.     

Electric field effects in the EPR spectrum of low-spin Ni<Superscript>3+</Superscript> centers in the KTaO<Subscript>3</Subscript> crystal

The electric field effects in the EPR spectra of low-spin (S = 1/2) Ni³⁺ tetragonal centers in KTaO₃ single crystals are investigated. It is revealed that the resonance lines are split and the centers are oriented as a result of the interaction of the external field with the electric dipole moment of the center. The dipole moment of the center is determined to be p = 100 D = 21 e?. An analysis of the set of experimental data obtained permits one to choose correctly the microscopic models for two nickel centers in KTaO₃ crystals among the models discussed in the literature. Original Russian Text ￠ L.S. Sochava, S.A. Basun, V.é. Bursian, A.G. Razdobarin, D.R. Evans, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 12, pp. 2157–2160.     

Electron paramagnetic resonance of Mn<Superscript>2+</Superscript> ions in single crystals of yttrium aluminum borate YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Single crystals of yttrium aluminum borate YAl₃(BO₃)₄ doped with manganese ions are studied using electron paramagnetic resonance spectroscopy. It is shown that manganese ions introduced at low concentrations into the sample predominantly occupy yttrium ion sites in the crystal structure. The shape of the electron paramagnetic resonance spectrum unambiguously indicates that the valence of manganese ions in this case is equal to 2+. The parameters of the spin Hamiltonian of Mn²⁺ ions in the YAl₃(BO₃)₄ matrix are determined at room temperature. The magnitude and sign of the fine structure parameter D allow the conclusion that the YAl₃(BO₃)₄ single crystals doped with manganese ions have a strong crystal field at the yttrium ion sites and easy-axis anisotropy.     

Theoretical study of photoionization of the isoelectronic sequence Rb<Superscript>+</Superscript>, Sr<Superscript>2+</Superscript>, and Y<Superscript>3+</Superscript>

The photoionization cross sections for the 4p shell of ions of the Kr isoelectronic sequence Rb⁺, Sr²⁺, and Y³⁺ are calculated. The configuration interaction theory and the perturbation theory are used to describe the many-electron effects. The relativistic effects are taken into account in the Pauli-Fock approximation. The calculated resonance structure of photoionization cross sections for the 4p shell in the region below the 4s threshold associated with the autoionization of the 4s-np singly excited states and the 4p4p-nln′l′ doubly excited states reproduces the results of recent measurements of total photoabsorption cross sections for the Rb⁺, Sr²⁺, and Y³⁺ ions. It is found that, as the nuclear charge in the isoelectronic sequence increases, the ratio between the direct and correlation parts of amplitudes of the 4s-(n/?)p transition changes and, as the consequence, the minimum of the photoionization cross section of the 4s shell shifts from the continuous spectrum to the region of states of discrete spectrum. This accounts for the strong changes in the shape of the 4s-np resonances in the photoionization cross sections for the 4p shell of Rb⁺, Sr²⁺, and Y³⁺, as well as the distinction between the shapes of the 4s-6p _1/2 mirror resonance in the partial 4p _1/2 and 4p _3/2 photoionization cross sections for the Y³⁺ ion which do not suppress each other in the total photoionization cross section, as is the case for similar resonances in Rb⁺ and Sr²⁺.     

Spin State of Co<Superscript>3+</Superscript> Ions in Layered GdBaCo<Subscript>2</Subscript>O<Subscript>5.5</Subscript> Cobaltite in the Paramagnetic Phase

A new scheme interpreting the changes in the spin state of Co³⁺ ions in GdBaCo₂O_5.5 in the course of the metal–insulator transition is proposed. The transition occurs gradually within a wide (~100 K) temperature range. The changes in the spin state of Co³⁺ ions are revealed using the data on the linear thermal expansion. In the metallic state, less than one-half of Co³⁺ ions are in the high-spin (HS, S = 2) state in octahedra, whereas the remaining ions are in the low-spin (LS, S = 0) state. The transition to the nonmetallic state occurs owing to the transformation of the HS state to the LS state in octahedra and to the transformation of some part of LS Со3+ in pyramids to the intermediate-spin (IS, S = 1) state.     

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.     

The influence of chromium impurity centers on the critical properties of a weakly polar ferroelectric Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript>

The Cr³⁺ EPR spectra of Li₂Ge₇O₁₅ (LGO) crystals are analyzed in the temperature range of the ferroelectric phase transition. The temperature dependence of the local order parameter is determined from the measured splittings of the EPR lines in the polar phase. The experimental critical exponent of the order parameter β=0.31 in the range from the phase transition temperature T _C to (T _C -T) ～ 40 K corresponds to the critical exponent of the three-dimensional Ising model. Analysis of the available data demonstrates that, away from the phase transition temperature T _C , the macroscopic and local properties of LGO crystals are characterized by a crossover from the fluctuation behavior to the classical behavior described in terms of the mean-field theory. The temperature dependence of the local order parameter for LGO: Cr crystals does not exhibit a crossover from the Ising behavior (β=0.31) to the classical behavior (β=0.5). This is explained by the defect nature of Cr³⁺ impurity centers, which weaken the spatial correlations in the LGO host crystal. The specific features of the critical properties of LGO: Cr³⁺ crystals are discussed within a microscopic model of structural phase transitions.     

Magneto-optical spectroscopy and optical detection of EPR spectra of Yb<Superscript>3+</Superscript> paramagnetic centers with cubic symmetry in single crystals <Emphasis Type="Italic">Me</Emphasis>F<Subscript>2</Subscript> (<Emphasis Type="Italic">Me</Emphasis> = Cd,Ca, Pb)

Cubic paramagnetic centers formed by Yb³⁺ impurity ions in fluorite-type crystals MeF₂ (Me = Cd, Ca, Pb) have been investigated using electron paramagnetic resonance, magnetic circular dichroism, magnetic circular polarization of luminescence, Zeeman splitting of optical absorption and luminescence lines, and optical detection of electron paramagnetic resonance. The g factors of the ²Γ₇ state in the excited multiplet ² F _5/2 of Yb³⁺ ions in Me F₂ crystals, the hyperfine interaction constant ¹⁷¹ A (¹⁷¹Yb) for the excited multiplet ² F _5/2 in the CaF₂ crystal, and the energies and symmetry properties of all energy levels of Yb³⁺ ions in MeF₂ crystals are determined. The crystal-field parameters for the crystals under investigation are calculated.