Specific features of optical absorption in rare-earth orthoaluminate DyAlO<Subscript>3</Subscript>

Polarization spectra of optical absorption of the 4f-4f transition ⁶ H _15/2 → ⁶ F _3/2 in the rare-earth orthoaluminate DyAlO₃ are theoretically and experimentally studied at the temperature T=78 K. It is shown that the nontrivial character of the anisotropy of the polarization absorption spectra at low temperatures can be explained by the J-J mixing of excited multiplets of the 4f ⁹ configuration of Dy³⁺ ions in a low-symmetry crystal field of the orthoaluminate structure. The energy and wave functions of the Stark sublevels within the excited ⁶ F _5/2 multiplet in the 4f ⁹ configuration of the Dy³⁺ rare-earth ion in the crystal field of C _s symmetry are numerically calculated.     

Determination of odd-symmetry crystal-field parameters from optical spectra

We have obtained analytical expressions for effective parameters of the crystal field that acts on spin-orbit multiplets of 4f ^N configurations taking into account admixture to them of 4f ^N?15d excited states and ligand-to-metal charge-transfer states. As an example, we analyze splittings of the ground and excited multiplets of Pr³⁺ and Tm²⁺ ions in some crystals without an inversion center. The effect of mixing of states of different configurations is most strongly pronounced for the ¹ G ₄ and ¹ D ₂ excited multiplets. The interconfigurational contribution to splittings is different for different multiplets. This circumstance makes it possible to estimate the values of the parameters of the odd-symmetry crystal field, which causes mixing of the 4f ^N and 4f ^N?15d states, and the covalence parameters of rare-earth ion-ligand bonds.     

Long-range coulomb interaction of electrons of 4f orbitals in impurity centers Yb3+: KZnF3, CsCaF3, and Sm3+: CaF2

Expressions for calculating the matrix elements of the Coulomb interaction of f electrons of the isolated ion with an infinite crystal lattice have been obtained. The contribution of this interaction to the parameters of the crystal field in impurity centers Yb³⁺: KZnF₃, CsCaF₃, and Sm³⁺: CaF₂ has been calculated.     

ESR of Yb3+ ions in a single crystal of the fluctuating-valence compound YbB12

The temperature and angular dependences of electron spin resonance (ESR) spectra of Yb³⁺ ions in a single crystal of fluctuating-valence compound YbB₁₂ were studied. The existence of Yb?Yb ion pairs was observed in a cubic-symmetry crystal. The ions forming the pairs are coupled by the isotropic exchange but interact also with the other pairs by the dipole and exchange coupling. The occurrence of a slight anisotropy in a cubic semiconductor may be the result of a spontaneous break of symmetry specific for the ground state of the Kondo dielectric. A strong temperature dependence of the amplitude of the ESR signals is found at 1.6–4.2 K and interpreted as a result of the capture of electrons by Yb³⁺ ions from electron traps with a binding energy of 18 K. ESR spectra of Yb³⁺ single ions in the Γ₆ state were observed also. The decrease of temperature from 4.2 to 1.6 K indicates a tendency to the ferromagnetic ordering of Yb?Yb pairs.     

Polarization selection rules for the allowed optical transitions in europium-terbium double activated calcium tungstate phosphor

The paper is devoted to the problem of the optical anisotropy of the rare-earth ions occupying low-symmetry positions in crystals. The crystal field multiplets arising from LSJ terms of Eu³⁺ and Tb³⁺ ions in the crystal field of calcium tungstate scheelite (CaWO₄) are analyzed (S₄ point symmetry). The selection rules, in particular, polarization rules for the allowed electric dipole optical transitions in the electronic shells of the Eu³⁺ and Tb³⁺ in CaWO₄ host lattice are discussed. Special attention is paid to the study of the angular (polarization) dependence of the two-photon absorption that seems to be an effective tool for the understanding of the complicated optical pattern. The peculiarities of the anisotropy of the two-photon absorption prove to be specific for each allowed dipole transition in S₄ symmetry center.     

Selective laser spectroscopy of Mn4+-Mn4+ pair centers in SrTiO3 crystal

Zero-phonon lines of a pair center of Mn⁴⁺ ions are observed in the luminescence and luminescence-excitation spectra of SrTiO₃:Mn crystal. Based on the experimental data, the energy-level structure of the ground state ∣⁴ A _2g ,⁴ A _2g 〉 and excited state ∣⁴ A _2g ,² E _g 〉 of the Mn⁴⁺-Mn⁴⁺ pair center is constructed. It is shown that the exchange interaction in the ground state of the Mn⁴⁺-Mn⁴⁺ pair is antiferromagnetic. Energies of the levels are calculated assuming that the pair is formed by Mn⁴⁺ ions occupying neighboring octahedral positions of Ti⁴⁺ ions along the [110] axis. Experimental values of the exchange integral in the ground state ∣⁴ A _2g ,⁴ A _2g 〉 and energies of spin multiplets in the excited state ∣⁴ A _2g ,² E _g 〉 agree well with calculation of the exchange interaction carried out within the framework of the channel model with the parameters J _ξη = 32 cm^4-1 and J _ζζ = ?45.5 cm^4-1. Experimental data and calculations unambiguously demonstrate that zero-phonon lines in the luminescence and luminescence-excitation spectra have magnetic-dipole nature.     

Spectra of optical absorption and energy levels diagram of Er<Superscript>3+</Superscript> ions in bulk crystals of aluminum nitride

The absorption spectra of the Er³⁺ ions embedded in the AlN matrix have been investigated. The admixture of erbium was introduced in bulk AlN crystals by diffusion. The absorption lines, which are associated with the intraconfigurational electronic f–f-transitions from the ground ⁴ I _15/2-state to the levels of ion Er³⁺ excited states have been observed in the spectral range of 370–700 nm. The transitions to the state levels ⁴ F _9/2, ² H _11/2, ⁴ F _7/2, ⁴ F _5/2, ² H _9/2, and ⁴ G _11/2 have been investigated in detail at the temperature T = 2 K. The number of the observed lines for these transitions coincides with the theoretically possible one for the electronic f–f-transitions in the ions Er³⁺, which are in the crystal field with the symmetry below cubic. The narrowness of the observed lines and their number convincingly testify the replacement of preferably one regular crystalline position by erbium ions. The implementation of Er³⁺ in the Al³⁺ position with the local symmetry C _3v appears the most probable. The energy positions of the levels of excited states for the investigated transitions have been determined. The diagram of the Er³⁺ ion energy levels in the AlN crystals has been built.     

Magnetic anisotropy of antiferromagnet (CH3)4NMnCl3

The parameters of the electron paramagnetic resonance (EPR) spectra of S ion pairs in diamagnetic crystals are analyzed. A relation between the spin Hamiltonian constants is established for solitary ions and pairs for (CH₃)₄NCdCl₃: Mn²⁺ crystals. In contrast to solitary ions, an additional contribution (which is a linear function of the exchange field) to the “single-ion” spin Hamiltonian constants appears in the case of pairs. It is shown that anisotropic exchange mechanisms do not play a significant part in the formation of the axial constant of the spin Hamiltonian for this crystal. Some aspects of the method of studying “single-ion” anisotropy predicted by the two-ion model are developed with the help of an isostructural diamagnetic analog with impurity concentration of the paramagnetic ions of a magnetically concentrated substance sufficiently high for observing the EPR spectrum of the pairs. It is found that the microscopic quantities determined partially from the EPR spectra for pairs and solitary Mn²⁺ ions in (CH₃)₄NCdCl₃ are in accord with the experimental value of the effective field for the (CH₃)₄NMnCl₃ crystal anisotropy which can be described primarily by the dipole and “single-ion” mechanisms of the exchange origin.     

Crystal field analysis of the ground and excited state absorption of a Cr<Superscript>4+</Superscript> ion in LiAlO<Subscript>2</Subscript> and LiGaO<Subscript>2</Subscript> crystals

The exchange charge model of crystal field theory has been used to analyze the ground and excited state absorption of tetrahedrally coordinated Cr⁴⁺ ion in lithium aluminum oxide LiAlO₂ (γ-phase) and lithium dioxogallate LiGaO₂. The parameters of the crystal field acting on the Cr⁴⁺ ion are calculated from the crystal structure data, taking into account the crystal lattice ions located at distances up to 12.744 Å in LiGaO₂ and 13. 180 Å in LiAlO₂. The obtained energy level schemes were compared with experimental ground and excited state absorption spectra and literature data on the application of other crystal field models (the angular overlap model and Racah theory) to the considered crystals; a good agreement with experimental data is demonstrated.     

Nephelauxetic effect for the isoelectronic 3d-ions (Cr, Mn, Fe) in SrTiO3

The exchange charge model of crystal field theory has been used to analyze systematically the ground state absorption spectra of isoelectronic Cr³⁺, Mn⁴⁺, and Fe⁵⁺ ions in an octahedral coordination in the SrTiO₃ crystal. The parameters of the crystal field acting on the valence electrons of impurity ions are calculated from the available crystal structure data. A special attention is paid to the analysis of dependencies of the crystal field invariants and covalence effects on the impurity ion. It is shown numerically that the covalence effects between the above impurity ions and ligands increase with an increase of the 3d-ion oxidation state.     

Crystal field effects on the saturation magnetic moment of Sm3+ ion in ferronagnetic samarium compounds

The effects of cubic crystal fields on the saturation magnetic moment of Sm³⁺ ion in ferromagnetic compounds have been investigated. In samarium compounds with magnetic elements, the exchange fieldH _ex acting on Sm³⁺ ion is taken to be proportional to the sublattice magnetization of the magnetic element, while in compounds with nonmagnetic elementsH _ex is taken to be proportional to the spin average of the Sm³⁺ ion and is determined self-consistently. In both types of compoundsH _ex is assumed to be along [001] direction. The saturation magnetic moment is calculated by taking into account the admixture of excited (J=7/2 andJ=9/2) levels into the ground (J=5/2) level of Sm³⁺ ion by crystal fields and exchange fields. It is shown that depending upon the strength, the crystal fields quench or enhance the magnetic moment from the free ion value, and in some cases force Sm³⁺ ion to behave effectively like an (L+S) ion rather than an (L−S)ion. The crystal fields may have important bearing on the performance of samarium compounds as permanent magnet materials.     

Absorptions- und Fluoreszenzspektren des Systems KCl:Sm2+ bei tiefen Temperaturen

Sharp emission line spectra of Sm²⁺ in KCl single crystals are observed up to 40 °K. From these it is possible to verify the idea of a substitution of a regular cation by an impurity ion and of a simultaneous association of a cation vacancy in the nearest neighbourhood [1/2 (110)]. This means that the crystal field at the place of the bivalent Samarium has the site symmetryC _2v . A cubic symmetry does not explain the spectra. It is possible to identify the line groups with the transitions, which are permitted by reason of the selection rules, and to set up the energy level diagram of the Sm²⁺ ion in KCl. The separation of the single impurity-vacancy complexes was reached by quenching the crystals from 650 °C to room temperature. The assumption of excitation exchange between neighbouring Samarium ions explains the spectra of the non-quenched crystals. The number of emission lines is determined for two different orientations of two dipole complexes towards one another. An interpretation of the absorption spectra of Sm²⁺ in KCl is proposed.     

Influence of magnetic ordering on electronic structure of Tb<Superscript>3+</Superscript> ion in TbFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> crystal

Optical absorption spectra of trigonal crystal TbFe₃(BO₃)₄ have been studied in the region of ⁷F₆ → ⁵D₄ transition in Tb³⁺ ion depending on temperature (2–220 K) and on magnetic field (0–60 kOe). Splitting of the Tb³⁺ excited states, both under the influence of the external magnetic field and effective exchange field of the Fe-sublattice, have been determined. Landé factors of the excited states have been found. Stepwise splitting of one of the absorption lines has been discovered in the region of the Fe-sublattice magnetic ordering temperature. This is shown to be due to the abrupt change of equilibrium geometry of the local Tb³⁺ ion environment only in the excited state of the Tb³⁺ ion. In general, the magnetic ordering is accompanied by temperature variations of the Tb³⁺ local environment in the excited states. The crystal field splitting components have been identified. In particular, it has been shown that the ground state (in D ₃ symmetry approximation) consists of two close singlet states of A ₁ and A ₂ type, which are split and magnetized by effective exchange field of the Fe-sublattice. Orientations of magnetic moments of the excited electronic states relative to that of the ground state have been experimentally determined in the magnetically ordered state of the crystal. A pronounced shift of one of absorption lines has been observed in the vicinity of the TbFe₃(BO₃)₄ structural phase transition. The temperature interval of coexistence of the phases is about 3 K.     

Analysis of Energy Transfer and Concentration Quenching in Sm3+-Activated Borate GdB3O6 Phosphors by Means of Fluorescence Dynamics

This article reports on the optical properties of Sm³⁺-activated GdB₃O₆ phosphors based on the measurement of their photoluminescence spectra and luminescence decay curves. Energy transfer from Gd³⁺ to Sm³⁺ and the concentration quenching of the Sm³⁺ ion emission are investigated. From the photoluminescence spectra and decay curves, the energy transfer from Gd³⁺ to Sm³⁺ is confirmed. The concentration quenching of the Sm³⁺ ion emission can be ascribed to resonant cross-relaxation. The interaction between the Sm³⁺ ions is derived of the electric dipole–dipole type through fitting the data with the Inokuti-Hirayama model. The critical distances and energy transfer microparameter for the transfer processes are given. The decay curves of Sm³⁺⁴G_5/2 level exhibiting a buildup and decay process also confirm the energy transfer from Gd³⁺ to Sm³⁺ and between Sm³⁺ ions.     

Bulk magnetization study of a DyNi5 single crystal

Magnetization and susceptibility measurements were performed on a single crystal of DyNi₅ along the three main symmetry axes of the ortho-hexagonal cell. Below its ordering temperature (T_c = 11.6 K), b and c are respectively the easy and hard magnetization axes. The strong anisotropy originates from the crystalline electric field acting on the 4f electrons of the Dy³⁺ ions. A small magnetization is induced on nickel atoms by the applied field and the exchange interactions with the dysprosium atoms. The crystal field parameters, the molecular field coefficients and the susceptibility of nickel atoms are determined from the experimental data.     

Investigations of the spin-Hamiltonian parameters for Er3+ ions in AlN crystal

The spin-Hamiltonian parameters (g factor g _//, g _⊥ and hyperfine structure constants A _//, A _⊥) for Er³⁺ ion at the trigonal Al³⁺ site of AlN crystal are calculated by diagonalising the 52 × 52 energy matrix. The matrix are related to the ground mutiplet ⁴I_15/2 and the first to third excited multiplets ⁴I_13/2, ⁴I_11/2 and ⁴I_9/2 for 4f¹¹ ions in trigonal crystal field under an external magnetic field. The crystal-field parameters used in the matrix are obtained from the superposition model and the local lattice relaxation due to the substitution of Er³⁺ for Al³⁺ is considered. The calculated spin-Hamiltonian parameters are in reasonable agreement with the experimental values and the signs of hyperfine structure constants are suggested. The results are discussed.     

On the theory of the direct excited exchange in Eu-chalcogenides

A mechanism of direct excited exchange between the nearest Eu²⁺ ions in Eu-chalcogenides caused by simultaneous electron 4f⁷ → 4f⁶5d¹ transitions on both ions is proposed. The wavefunctions are considered, the energy spectrum is found, and the form of effective spin-Hamiltonian is determined for the Eu²⁺ ? Eu²⁺ “molecule” in crystal field of D_2h symmetry. The change of effective exchange integral between nearest Eu²⁺ ions in a series of Eu-chalcogenides is discussed briefly.     

Absorptionsspektren von Er3+ in InCl3 und in ScCl3

The optical absorption spectra of Er³⁺ in single crystals of InCl₃ and ScCl₃ have been obtained between 14,000 and 29,000 cm^?1. The observed crystal field splittings are interpreted in terms of crystal potential of symmetry 3m for ScCl₃ and of symmetry 2m for InCl₃. There is however found, that for both cases the splittings will be approximately explained by a crystal potential of cubic symmetry. The employed hostlattices are of special interest, because the ions of the iron series can occupy the same sites as the rare earth ions.     

Quantum theory of the magneto-optical effect and magnetization of Nd-substituted yttrium iron garnet

The magneto-optical and magnetic properties of Nd ³⁺ ions in Y ₃Fe ₅O ₁₂ garnet are analyzed by using quantum theory. In the spontaneous state, the magneto-optical effects originate mainly from the intra-ionic electric dipole transitions between the 4 f ³ and 4 f ²5d states split by the spin-orbit, crystal field, and superexchange interactions. For the excited configuration, the coupling scheme of Yanase is extended to the Nd ³⁺ ion. The magneto-optical resonance frequencies are mainly determined by the splitting of the 5d states induced by the crystal field. The theoretical results of both Nd magnetization and Faraday rotation are in good agreement with experiments. The observed Faraday rotation is proved to be of the paramagnetic type. Although the value of the magneto-optical resonance frequency derived from a macroscopic analysis is approximately confirmed by our theoretical study, a new assignment about the transitions associated with this resonance is unambiguously determined. The spin-orbit coupling of the ground configuration has a great influence on both the Faraday rotation and magnetization, but, unlike the theoretical results obtained in some metals and alloys, the relation between the Faraday rotation and the spin-orbit coupling strength is more complex than a linear one. The magnitude of the magneto-optical coefficient increases as the spin-orbit interaction strength of the ground configuration decreases when the strength is not very weak. Finally, the temperature dependence of the magneto-optical coefficient and the effect of the mixing of different ground-term multiplets induced by the crystal field are analyzed. Received 8 November 2000