EPR,ENDOR and optical spectroscopy of Yb3+ ion in KZnF3 single crystals

The paramagnetic center of tetragonal symmetry formed by the Yb³⁺ ion in the KZnF₃ crystal has been studied using methods of EPR, ENDOR and optical spectroscopy. The location of the impurity ion and the structural model of the complex differing from the model of the Yb³⁺ center in KMgF₃ have been established. The empirical scheme of the energy levels of the Yb³⁺ ion has been found. The parameters of its interaction with the crystal electrostatic field and the hyperfine interaction with ligands of the nearest environment have been determined. The parameters of the crystal field were used for the analysis of the distortions of the crystal lattice in the vicinity of Yb³⁺. The parameters of the transferred hyperfine interaction have been calculated for the distances between Yb³⁺ and F⁻ ions of the nearest environment obtained taking into account the found distortions. They are in good agreement with the experimental values.     

EPR and optical spectroscopy of the Tm2+ ion in the KMgF3 single crystal

Paramagnetic Tm²⁺ ion centers in the KMgF₃ single crystal have been studied by electron paramagnetic resonance and optical spectroscopy. The Stark level energies of the cubic Tm²⁺ multiplets have been established from the luminescence spectra and the crystal field parameters have been calculated. Information about the phonon spectra of KMgF₃ crystals has been obtained from the electron-vibrational structure of the optical luminescence spectra.     

Optical spectra of octahedral cubic and trigonal Yb3+ impurity centers in KMgF3 and KZnF3 crystals

Groups of lines corresponding to octahedral cubic and trigonal impurity centers have been isolated in complex many-center luminescence and excitation spectra of Yb³⁺-doped KMgF₃ and KZnF₃ crystals. The crystal-field potentials derived from the spectra are in good agreement with those of similar centers in CsCaF₃:Yb³⁺ crystal studied earlier. Fiz. Tverd. Tela (St. Petersburg) 40, 2029–2034 (November 1998)     

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.     

Formation of new Tm3+ tetragonal symmetry optical centers in CaF2 hot-formed laser ceramics

By means of time-resolved site-selective spectroscopy the formation of new Tm³⁺ optical centers with modified local environment and presumably tetragonal local symmetry in CaF₂ hot-formed laser quality ceramics is observed. The spectroscopic properties of these new Tm³⁺ optical centers are investigated and shown to differ strongly from that for regular tetragonal optical centers.

     

KZnF3:Cr3+和KMgF3:Cr3+四角对称电子顺磁共振参量与晶格缺陷的研究

用Newman叠加模型研究了KZnF₃:Cr³⁺四角对称基态的零场分裂,证实了Zn²⁺空位和畸变的存在;并指出,空位对晶场的贡献不可忽略。计算得到:KZnF₃:cr³⁺晶体[0,01]方向的一个F^-配体向Cr³⁺移动Δ(KZnF₃)=0.0029-0.0043nm。还研究了KMgF₃:Cr^{3+关键词：}     

EPR and optical spectroscopy of Yb3+ ions in single crystal CsCaF3

CsCaF₃ crystals doped with Yb³⁺ were studied using EPR and optical spectroscopy methods. Several types of paramagnetic centers of Yb³⁺ were found including a paramagnetic center in an uncommon 12-coordinated position. The schemes of the energy levels of the observed centers are determined and the potentials of the respective crystalline fields are calculated.     

Crystal field of octahedral Yb3+ centers in a CsCaF3 crystal

The phenomenological crystal-field potentials of cubic and trigonal Yb³⁺ centers in a CsCaF₃ crystal have been determined from the experimental energy-level schemes. These potentials are compared with the potentials of the analogous centers in the isomorphic hosts KMgF₃ and KZnF₃. Information about the phonon spectrum of a CsCaF₃:Yb crystal was obtained from the electronic-vibrational structure of the luminescence spectra. Fiz. Tverd. Tela (St. Petersburg) 39, 1030–1034 (June 1997)     

Theoretical studies of the dependence of EPR g-factors on local structure for the trigonal Er3+–VK centres in KMgF3 and KZnF3

The dependence of the EPR g-factors on the local structural parameter for a 4f¹¹ configuration ion Er³⁺ in a trigonal crystal-field has been studied by diagonalizing the 364×364 complete energy matrices. Our studies indicate that the EPR spectra of the trigonal Er³⁺–V_K centers in KMgF₃ and KZnF₃ may be attributed to the translation of the cubic Kramers doublet Γ₇. Furthermore, the EPR g-factors of the trigonal Er³⁺–V_K centers may be interpreted reasonably by the shifts ΔZ≈0.340 Å and ΔZ≈0.303 Å of the Er³⁺ ions toward the charge compensator V_K along the C₃ axis for the KMgF₃:Er³⁺ and the KZnF₃:Er³⁺ systems respectively.     

Determination of the Position of the Impurity Yb3+ ion in the CsCaF3 crystals

CsCaF₃ crystals doped with Yb³⁺ ions have been studied using the electron paramagnetic resonance and optical spectroscopy methods. Several types of paramagnetic Yb³⁺ centers were found, among which a paramagnetic center in the unusual position was established. The parameters of the corresponding spin Hamiltonians and schemes of the energy levels of the observed centers were determined.     

Bilinear and biquadratic exchange interactions and their effect on magnetic susceptibilities of KMgF3: Mn and KZnF3: Mn

Exchange interaction constants of nearest (J₁) and next-nearest-neighbor (J₂) Mn²⁺ in KMgF₃: Mn and KZnF₃: Mn have been evaluated from the magnetic susceptibilities. For KZnF₃: Mn, J₁ = 8.2 ± 0.5 K; this is consistent with the ESR value if biquadratic exchange is present.     

Study of the Structures of the Tetragonal Paramagnetic Centers in the Mixed Fluorite Crystals with Rare-Earth Ions by EPR

Electron paramagnetic resonance (EPR) of the mixed fluorite crystals with the general formula (MeF₂)_1?x?y (REF₃) _x (RF₃) _y (Me = Ca, Sr, Ba; R = Y, La, Lu; RE—paramagnetic trivalent rare-earth ions) were studied comprehensively by different authors and several structural models of paramagnetic centers were considered. However, a lot of details of EPR spectra still remain unexplained. In this work some modifications of the simplest models are proposed which allow explaining adequately the variety of the tetragonal centers in crystals grown under the different conditions. The calculated from the proposed models components of g-factors for Ce³⁺, Nd³⁺, Sm^3+, Er³⁺ ions are in a good agreement with the experimental values.     

Superhyperfine Structure of the EPR Spectra of Nd<Superscript>3+</Superscript> Impurity Ions in Fluorite CaF<Subscript>2</Subscript>

EPR spectra of a CaF₂ single crystal that was grown from melt containing a small addition of NdF₃ were studied. Signals corresponding to tetragonal centers of Nd³⁺ ions and cubic centers of Er3+ and Yb3+ ions were found. Superhyperfine structure (SHFS) in the spectra of the Nd³⁺ ions was observed for the first time in this crystal; parameters of the superhyperfine interaction of the Nd³⁺ ions with the nearest nine fluorine ions were determined. The dependence of the resolution of the Nd³⁺ EPR spectrum SHFS on the incident microwave power at the temperature of T ≈ 6 K was studied. Obtained results are discussed and compared with the literature data.     

Local structure of titanium pair centers in SrF2 crystals: EPR and ENDOR spectroscopic studies

The local structure of titanium pair centers in SrF₂: Ti crystals is investigated using electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy. It is found that titanium pair centers with spin moment S=2 and tetragonal symmetry of the magnetic properties are formed in SrF₂: Ti cubic crystals under certain growth conditions and during annealing. The tensor components of the fine and ligand hyperfine structures in the EPR and ENDOR spectra are determined. A model of the Ti⁺-Ti³⁺ paramagnetic dimer is proposed. This model provides an adequate interpretation of both the ferromagnetic nature of the exchange interaction and the observed displacements of four ligands in the first coordination sphere of titanium impurity ions in directions perpendicular to the impurity ion-ligand bonds.     

Microstructure of pair centers of Cr3+-Cr2+ ions in the KZnF3 crystal

Studies involving the piezospectroscopy method have shown that the symmetry of the pair centers of Cr³⁺-Cr²⁺ ions in the KZnF₃ crystal is tetragonal. In this paper we develop a microscopic model of a pair center. We use the temperature dependence of the integrated intensity of the absorption line to find the effective hopping integral for an e _g electron, t _σσ=205 ± 10 cm⁻¹, and the polaron reduction factor, equal to 0.11. By analyzing the selection rules for exchange-induced electric dipole transitions under double-exchange conditions we identify all the absorption lines of Cr³⁺-Cr²⁺ pairs. Zh. éksp. Teor. Fiz. 114, 1421–1429 (October 1998)     

EPR and optical spectroscopy of Yb<Superscript>3+</Superscript> ions in CaF<Subscript>2</Subscript>: an analysis of the structure of tetragonal centers

CaF₂ crystals doped with Yb³⁺ ions have been studied by electron paramagnetic resonance (EPR) and optical spectroscopy. EPR spectra of paramagnetic centers (PCs) for cubic (T_c) and tetragonal (T_tet) symmetries were identified. Empirical energy level diagrams were established and crystal field parameters were determined. Information on the CaF₂∶Yb³⁺ phonon spectra was obtained from the electron-vibrational structure of the optical spectra. The crystal field parameters were used to analyze the crystal lattice distortions in the vicinity of the Yb³⁺ ion. Within the framework of a superposition model, it is established that four F⁻ ions located symmetrically with respect to the fourfold axis from the side of the ion-compensator approach the impurity ion and deviate from the PC axis. The second set of four fluorine ions also approaches the Yb³⁺ ion and the PC axis. The ion-compensator F⁻ also approaches considerably the impurity ion.     

Optical spectra of nearest neighbour nickel pairs in KMgF3 and KZnF3 crystals

The absorption, MCD, and emission spectra associated with the nearest neighbour Ni²⁺ pairs in KMgF₃ and KZnF₃ have been studied and analysed on the basis of the theory which includes spin dependent excitation transfer as well as spin independent transfer. It is shown that excitation transfers are important in determining the pair energy levels for the case where the singleion states involve orbital degeneracy. The antiferromagnetic J value of the ground state is determined to be 68 cm^-1.     

Algebraic method of determining bond length of perovskite compounds doped with Mn

An algebraic method is proposed for calculating the exponent n and constant K in the power law 10Dq=KR⁻ⁿ. By using this method, the values of n and K for the cubic perovskites KMnF₃ and RbMnF₃ are derived and then used to determine the true Mn²⁺–F⁻ bond length R in crystals of KMgF₃, KZnF₃, RbCdF₃, and CsCaF₃ doped with Mn²⁺ from the reported optical spectra. The results obtained are in good agreement with those derived from the electron paramagnetic resonance data and the extended X-ray absorption fine structure techniques. Thus, as a new theoretical method, it is valuable and convenient for the determination of the bond lengths.     

EPR of Er3+, Nd3+, and Ce3+ ions in YAlO3 single crystals

EPR spectra of the Er³⁺, Nd³⁺, and Ce³⁺ ions substituting for the Y³⁺ ion in the YAlO₃ yttrium orthoaluminate lattice are studied. The EPR spectra of these rare-earth ions are described by a spin Hamiltonian of rhombic symmetry with an effective spin S=1/2. The principal values of the g tensors were determined from an analysis of the angular dependences of the EPR spectra. The orientation of the local magnetic axes of paramagnetic centers relative to the YAlO₃ crystallographic directions are shown to depend on the actual rare-earth species. The EPR spectra exhibit a hyperfine structure due to the ¹⁶⁷Er, ¹⁴³Nd, and ¹⁴⁵Nd odd isotopes, which permitted unambiguous identification of these spectra. The hyperfine coupling constants for the odd erbium and neodymium isotopes are determined.     

Electron paramagnetic resonance of Gd3+ ions in Ca1 − x − y Y x Gd y F2 + x + y crystals

Electron paramagnetic resonance of Ca_{1 ? x ? y} Y _x Gd _y F_{2 + x + y} single crystals has revealed spectra that are not typical of gadolinium-doped CaF₂ crystals. These spectra have a nearly tetragonal symmetry and are most probably caused by Gd³⁺ ions localized in yttrium clusters. Weak spectra of tetragonal Gd³⁺ centers, whose parameters are close to those of a cubic gadolinium center caused by an isolated Gd³⁺ ion, have been also detected. These centers are attributed to isolated Gd³⁺ ions localized near octahedral rare-earth clusters or their associations.