Quadratic crystal field tensors and spin Hamiltonian tensors of Fe3+ in Li2Ge7O15 above and below the phase transition temperature

Dopant Fe³⁺ ions in tetrahedral and octahedral positions of Ge⁴⁺ in the crystal Li₂Ge₇O₁₅ were studied using EPR. Fe³⁺ substitutes for Ge⁴⁺ with a local charge compensation. The octahedral site and the tetrahedral sites significantly differ by the value of the invariant sumS(B ₄) of theB ₄ tensor of the spin Hamiltonian of Fe³⁺. The irreducible tensor products {V ₄ ? V ₄}₄ and {V ₄?V ₄}₂ theV ₄ tensor of the crystal field calculated using the point-charge model for octahedral and tetrahedral complexes provide the predominant contribution of the crystal field to theB ₄ andB ₂ tensors of the spin Hamiltonian of Fe³⁺, respectively. A comparison of the fourth-rank tensorsB ₄ of the spin Hamiltonian and {V ₄?V ₄}₄ of the crystal field determined at 300 K with those determined at 77 K supports the conclusion that the phase transition is accompanied by combined rotation of the [GeO₄] tetrahedra with the [Ge(1)O₆] octahedron almost unaltered. The spectrum lines are narrow and the variety of point defects in the vicinity of the paramagnetic impurity ions Fe³⁺, Cr³⁺ and Cu²⁺ is not detected. These facts are inconsistent with the statistically distributed model for the Li(2) atom. In specific cases at 300 K, when the wings of the two spectrum lines of theM→M+1 and theM+2 →M+3 transitions of Fe³⁺ ions belonging to one system of translationally equivalent positions overlap an extra line appears in the center between these lines. It is suggested that this effect is due to the soft phonon mode above the phase transition temperature.     

Low-symmetry spin hamiltonian and crystal field tensors analysis: Fe(3+) in natrolite

Electron paramagnetic resonance study of a natural single crystal of natrolite was carried out at the frequency nu=36.772 GHz at room temperature. The angular dependence of the four symmetry-related spectra of Fe(3+) in the three crystallographic planes was fitted to a spin Hamiltonian (S=5/2) of symmetry C(i). The rank 4 crystal field tensors at tetrahedral sites were calculated using the point-charge model to determine the principal axes orientations of their cubic and trigonal components. The analysis of zero-field splitting tensors and comparison with crystal field ones suggests that Fe(3+) substitutes for Al(3+) with no significant distortion of the coordination tetrahedron in natrolite. Comparison of data for several natural and synthetic crystals reveals that the 4-rank zero-field splitting tensor invariants for Fe(3+) at the tetrahedral oxygen-coordinated sites are distinguishably smaller than those for Fe(3+) at octahedral sites. Such comparative analysis may help to determine the substitutional sites in other crystals.     

EPR of Gd3+ in single crystal colquiriite and analysis of the spin Hamiltonian tensorsB 4 andB 6

In single crystal colquiriite LiCaAlF₆ doped with Gd³⁺ ions two EPR spectra of the Gd³⁺ ions with the Laue site-symmetry groups C_i and C_3i were observed. The spectrum angular dependence for trigonal Gd³⁺ centre was investigated in detail and corresponding spin Hamiltonian parameters were fitted. From analysis of the spin Hamiltonian tensorsB ₄ andB ₆ it was established that Gd³⁺ with the Laue group C_3i substitutes at Ca²⁺ site with the excess charge compensation by an ion located along the threefold axis from this site. The transformation formulas for a sixth-rank irreducible Hermitian tensor under coordinate rotation are tabulated in an explicit form. By using the EPR data for Gd³⁺ substituted in a variety of host crystals, the fourth-rank and sixth-rank tensors of Gd³⁺ spin Hamiltonians were tabulated and correlated with structures of the coordination polyhedra at substitution sites. The results suppose a predominance of quadratic crystal field contributions into the spin Hamiltonian tensorB ₄ of Gd³⁺.     

Electronic structure and spectrum of Cr3+ in LiCaAlF6

The electronic structure and spectrum of Cr³⁺ in LiCaAlF₆ are investigated by using the discrete variatitional-local density functional (DV-LDF) method with embedded cluster model. The clusters (CrF₆)^3– withC ₃,D _3d andO _h point group symmetries embedded in the crystal are treated. The one-electron energy levels, densities of states, orbital populations, spin polarization splittings and energies of some terms are calculated. The results show that the relaxation of F^– ions around the Cr³⁺ impurity is inevitable, and that theD _3d andO _h (CrF₆)^3– clusters, with an extended bond-lengthR(Cr–F) chosen to be equal to 1.88 Å can represent this relaxation in a much better way. All the ligand-field transition energies, which are obtained from the transition-state energy and the Griffith parameters, as yielded by a restricted one-electron DV-LDF calculation, compare well with the experimental ones.     

Ce3+∶LiCaAlF6紫外激光器的研究

报道了利用Nd∶YAG四倍频266 nm脉冲激光端面泵浦Ce∶LiCAF晶体，采用平凹谐振腔，输出296 nm波长紫外激光.当输出镜透过率为20％，入射泵浦能量为13.5 mJ时，获得最大输出激光脉冲能量为270 μJ，脉冲宽度为3.4 ns，输出激光峰值功率为79.4 kW，光－光转换效率为2%，斜效率为1.6％.     

Cr~（3＋）：LiCaAlF_6晶体的缺陷

观察并分析了Ｃｒ３＋：ＬｉＣａＡｌＦ６晶体中的缺陷，发现其中主要包括组分过冷、不定形固体颗粒和异相微晶颗粒等三类包裹体。此外，缺陷的宏观分布与生长方向有关。最后，讨论了缺陷的产生机理和消除途径。     

Theoretical evaluation of the electron paramagnetic resonance spin Hamiltonian parameters for the impurity displacements for Fe3+ and Ru3+ in corundum

The impurity displacements for Fe³⁺ and Ru³⁺ in corundum (Al₂O₃) are theoretically studied using the perturbation formulas of the spin Hamiltonian parameters (zero-field splitting and anisotropic g factors) for a 3d⁵ (with high spin S = 5/2) and a 4d⁵ (with low spin S = 1/2) ion in trigonal symmetry, respectively. According to the investigations, the nd⁵ (n = 3 and 4) impurity ions may not locate at the ideal Al³⁺ site but undergo axial displacements by about 0.132 Å and 0.170 Å for Fe³⁺ and Ru³⁺, respectively, away from the center of the ligand octahedron along the C₃ axis. The calculated spin Hamiltonian parameters based on the above axial displacements show good agreement with the observed values. The validity of the results is discussed.     

Local structure distortion and spin Hamiltonian parameters for Cr3＋-Vzn tetragonal defect centre in Cr3＋ doped KZnF3 crystal

The quantitative relationship between the spin Hamiltonian parameters (D, g_‖, Δg) and the crystal structure parameters for the Cr³⁺—V_Zn tetragonal defect centre in a Cr³⁺:KZnF₃ crystal is established by using the superposition model. On the above basis, the local structure distortion and the spin Hamiltonian parameter for the Cr³⁺—V_Zn tetragonal defect centre in the KZnF_3 crystal are systematically investigated using the complete diagonalization method. It is found that the V_Zn vacancy and the differences in mass, radius and charge between the Cr³⁺ and the Zn²⁺ ions induce the local lattice distortion of the Cr³⁺ centre ions in the KZnF₃ crystal. The local lattice distortion is shown to give rise to the tetragonal crystal field, which in turn results in the tetragonal zero-field splitting parameter D and the anisotropic g factor Δg. We find that the ligand F^- ion along [001] and the other five F^- ions move towards the central Cr³⁺ by distances of Δ₁ = 0.0121 nm and Δ₂ = 0.0026 nm, respectively. Our approach takes into account the spin—orbit interaction as well as the spin—spin, spin—other-orbit, and orbit—orbit interactions omitted in the previous studies. It is found that for the Cr³⁺ ions in the Cr³⁺:KZnF₃ crystal, although the spin—orbit mechanism is the most important one, the contribution to the spin Hamiltonian parameters from the other three mechanisms, including spin—spin, spin—other-orbit, and orbit—orbit magnetic interactions, is appreciable and should not be omitted, especially for the zero-field splitting (ZFS) parameter D.     

LiSrAlF6晶体Cr3+掺杂中心电子结构的研究

使用离散变分方法(DVM)对LiSrAlF6晶体中以Cr3+为中心的多种分子团簇的电子结构进行了计算.主要研究了镶嵌势、团簇大小、基组类型对单电子能量本征值、基态原子轨道特性的影响,给出了使计算结果趋于收敛的基本条件.     

EPR of trivalent iron ions in a LiCaAlF6 crystal

The orientational dependences of the EPR spectra of Fe³⁺-doped LiCaAlF₆ single crystals (space group P31c, Z=2), grown at the Laboratory of Magnetic Radio Spectroscopy at Kazan’ State University, have been investigated in detail. The spectrum is described by a trigonal spin Hamiltonian with the following parameters: B ₂₀=40.072×10⁻⁴ cm⁻¹, B ₄₀=−5.799×10⁻⁴ cm⁻¹, B ₄₃=−4.281×10⁻⁴ cm⁻¹, A _s=24.33±1, A _p=6.13±1, g _∥=g _⊥=2.00217±0.0003. A theoretical calculation of the hyperfine structure parameters shows that they are described quite well when allowance is made for the overlapping of the wave functions of the paramagnetic center and the ligands (F⁻). Fiz. Tverd. Tela (St. Petersburg) 39, 488–490 (March 1997)     

5d–4f luminescence of Ce3+, Gd3+ and Lu3+ in LiCaAlF6

The emission and excitation spectra as well as decay kinetics of luminescence due to 5d–4f transitions in Ce³⁺, Gd³⁺ and Lu³⁺ ions doped into LiCaAlF₆ crystals have been analyzed with high spectral and time resolution using synchrotron radiation for excitation. The rich fine structure originating from electronic origins of transitions and their phonon replica has been well resolved and identified. Experimental data are compared with the spectra simulated in the framework of the semiphenomenological models of the crystal field and the crystal lattice dynamics.     

Hyperfine field and diffusion of μ+ in Fe single crystals

In recent positive-muon spin rotation experiment at TRIUMF on single crystal Fe, a clear temperature dependent change has been observed, for the first time, both in frequency and depolarization rates from 300 K down to 23 K. The μ⁺ depolarization was explained by the μ⁺ diffusion through inhomogeneous dipolar fields and the diffusion constant was found to obey an Arrhenius law (activation energy 17 meV) above 70 K but surprisingly deviated from this at lower temperatures, indicating quantum diffusion. We have also found that the μ⁺ hyperfine field has a temperature dependence slightly stronger than that of the magnetization.     

Growth and radioluminescence of metal elements doped LiCaAlF6 single crystals for neutron scintillator

The ns²-type metal elements (Pb and Sn) doped LiCaAlF₆ single crystals were grown by a micro-pulling-down (μ-PD) method. Pb doped LiCaAlF₆ [Pb:LiCAF] crystals showed high transparency and single phase of the LiCAF structure. However, we could not obtain Sn:LiCAF crystals due to the evaporation of SnF₂ during the crystal growth. There was an absorption peak around 193 nm in the transmittance spectrum of Pb:LiCAF crystal. In the radioluminescence spectrum of the Pb:LiCAF crystal under X-ray irradiation, two emission peaks around 200 and 830 nm were observed.     

Group analysis of Nd3+ energy spectrum in crystal field

A theoretical analysis is made of the influence of the crystal field with cubic, hexagonal, tetragonal and trigonal symmetries on the lifting of the degeneracy of the free Nd³⁺ ion energy levels and at the same time the selection rules are determined for the dipole and quadrupole transitions between the split levels for the above symmetries.     

Angular dependence of the thermal-lens effect on LiSrAlF6 and LiSrGaF6 single crystals

We apply thermal-lens (TL) spectrometry to measure the angular dependence of the TL effect on colquiriite single crystals. The experiments were performed with LiSrAlF(6) and LiSrGaF(6) using a two-beam mode-mismatched configuration. The results show that it is possible to minimize the TL effect by selecting the appropriate crystal orientation. Our data also show that the anisotropy of the linear thermal expansion coefficient drives the amplitude of the TL effect, including the inversion from focusing to defocusing as the crystal orientation angle tends to the c-axis direction. The results may be useful for those working to develop a high-power laser using LiSrAlF(6)(:Cr) and LiSrGaF(6)(:Cr) single crystals, allowing for optimization of the designed laser cavity.     

Evaluation of Ce3+ and alkali metal ions Co-doped LiSrAlF6 crystalline scintillators

High scintillation efficiency of Eu-doped LiSrAlF₆ (LiSAF) and LiCaAlF₆ (LiCAF) codoped with alkali metal ions has been reported in our recent studies. Thus in this paper, we demonstrated the scintillation properties of 1% Ce-doped LiSAF crystals with 1% alkali metal ions co-doping to increase the light yield and understand the scintillation mechanism. The crystals showed intense emission band corresponding to the 5d-4f transition of Ce³⁺, and their light yields under thermal neutron excitation were higher than that of the Ce only doped crystal. Especially, the light yield of Ce–Na co-doped crystal exceeded about two times that of Ce only doped one.