G. S. Shakurov

Crystal Fields of Hexameric Rare-Earth Clusters in Fluorites

In solid solutions of alkaline-and rare-earth fluorides with a fluorite structure, ions of most elements of the rare-earth (RE) row form hexameric clusters that assimilate the minor component of the solid solutions (fluorine) and build it into the cubic fluorite lattice without changing its shape. An analysis of the EPR spectra of paramagnetic RE ions (Er3+, Tm3+, Yb3+) in clusters of diamagnetic ions (Lu3+, Y3+) confirms their hexagonal structure, which was established when studying the superstructures of the compounds under study. In such a cluster, a RE ion is in a nearly tetragonal crystal field, with the parameters of this field differing radically from those of single cubic and tetragonal RE centers in crystals with a fluorite structure. In particular, this field causes high (close to limiting) values of the g∥ factors of the ground states of the paramagnetic RE ions. Computer simulation is used to determine the atomic structure of a hexameric cluster in MF2 crystals (M = Ca, Sr, Ba). The crystal field and energy spectrum of Er3+, Tm3+, and Yb3+ ions in such clusters are calculated, and the spectroscopic parameters of the ground states of these ions are determined. The calculations confirm the earlier assumption that the unusual EPR spectra of nonstoichiometric fluorite phases are related to RE ions in hexameric clusters.

High-frequency EPR of Cr2+ ions in CdGa2S4

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 + B20O20 + B40O40 + B44O44 with the parameters B20=23659±2 MHz, B40=1.9±1 MHz, |B44|=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.

High-frequency tunable EPR spectroscopy of non-Kramers ions in AgGaSe2: Cr, AgGaS2: Cr, and CdGa2S4: Cr crystals

Crystals of the chalcopyrite family, AgGaSe2, AgGaS2, and CdGa2S4, doped with chromium ions have been investigated using high-frequency broad-band EPR spectroscopy in the range 65–530 GHz at T = 4.2 K. It has been revealed that, in the AgGaSe2 and AgGaS2 crystals, the Cr2+ ions occupy positions with orthorhombic and tetragonal symmetry, whereas the previously investigated CdGaS4 crystals contain only tetragonal centers. The observed spectra have been described in the framework of the spin-Hamiltonian formalism. Apart from the divalent chromium centers, the EPR lines attributed to non-Kramers ions are observed in the frequency range 300–450 GHz for all the crystals under investigation. The nature of these lines has been discussed.

Jahn-teller chromium ions in CdF2 and CaF2 crystals: An EPR spectroscopic study in the frequency range 9.3–300 GHz

The bivalent chromium impurity centers in CdF2 and CaF2 crystals are investigated using electron paramagnetic resonance (EPR) in the frequency range 9.3–300 GHz. It is found that Cr2+ ions in the lattices of these crystals occupy cation positions and form [CrF4F4]6− clusters whose magnetic properties at low temperatures are characterized by orthorhombic symmetry. The parameters of the electron Zeeman and ligand interactions of the Cr2+ ion with four fluorine ions in the nearest environment are determined. The initial splittings in the system of spin energy levels of the cluster are measured.

Paramagnetic resonance of yttrium aluminum garnet doped with 151Eu2+ ions

The 151Eu2+ orthorhombic centers in yttrium aluminum garnet crystals have been investigated. The initial splitting and hyperfine interaction parameters have been obtained taking into account the positions of the hyperfine structure components. The relative signs of the fine and hyperfine structure parameters have been determined from the analysis of the type of the hyperfine structure formed by the allowed and forbidden electron–nuclear transitions.

Wide-band EPR spectroscopy of YAlO3: Tm3+ single crystals

The YAlO3: Tm3+ single crystal has been studied on a wide-band EPR spectrometer. The EPR spectra of Tm3+ ions in the frequency range of 90–160 GHz have been detected for the first time. It has been confirmed that thulium ions substitute the position of Y3+ in the crystal lattice. The detected spectra have been described with the use of a spin Hamiltonian with the effective spin S = 1/2. A comparative analysis of the orientation of the magnetic axes of the Tm3+ paramagnetic center with earlier data on other rare-earth ions has been performed.

Low-energy excited states of 3d transition metal ions in zinc selenide

The results of studying the impurity heat capacity of Zn1−xMxSe (M = Cr2+, Fe2+, Ni2+, Mn2+) solid solutions in the temperature range 1.8–20.0 K are presented. A heat-capacity method is described and applied for the measurement of the intracenter-transition energy in these systems. The role of the Jahn-Teller effect in the formation of low-energy excited states of 3d ions in ZnSe is discussed.

Paramagnetic defects in ZnSe crystals doped with iron ions

The electron paramagnetic resonance (EPR) spectra of iron-doped ZnSe single crystals were studied. In addition to cubic Fe3+ and Mn2+ centers and also Fe2+, and Cr2+ centers, monoclinic Fe3+ complexes locally compensated by Cu+ ions were revealed. Some trigonal centers with a spin of 3/2 were also found and studied. The zero-field splittings of monoclinic centers were measured, and the parameters of the monoclinic and trigonal spin Hamiltonians were determined. The nature of trigonal centers was discussed.

Wideband EPR Spectroscopy of Mo3+ Ions in Yttrium–Aluminum Garnet

The crystals of yttrium–aluminum garnet with an admixture of iron and cerium have been studied by the method of wideband EPR spectroscopy. Resonance absorption of microwave radiation in the frequency range 220–300 GHz was detected. Based on the experimental data set, it is concluded that the signals belong to the Mo3+ ion, which is included in the crystals as an uncontrolled impurity. A straightforward method was used to measure the splitting in a zero field between the Kramers doublets |±1/2〉 and |±3/2〉 (261.6 ± 0.5 GHz). The calculated angular and frequency-field dependences of the EPR spectra are in good agreement with the experiment.

Submillimeter ESR spectra of Fe 2+ ions in synthetic and natural beryl crystals

Electron spin resonance spectra of non-Kramers bivalent iron (Fe2+) ions have been detected in synthetic and natural beryl crystals with an iron impurity. The observed ESR spectra have been attributed to resonance transitions of Fe2+ ions from the ground (singlet) state to excited (doublet) levels with the splitting Δ = 12.7 cm–1 between the levels. The experimental angular and frequency dependences of the resonance field of the ESR signal have been described by the spin Hamiltonian with the effective spin S = 1. The analysis of the ESR data and optical absorption spectra indicates that the Fe2+ ions are situated in tetrahedral positions and substitute Be2+ cations in the beryl structure.