晶体NiX2(X=Cl,Br,I)的光谱和电子顺磁共振谱研究

在强场耦合图像中,采用双自旋-轨道耦合(SO)参量模型建立了过渡族3d2(3d8)离子的三角对称下全组态光谱能级和电子顺磁共振(EPR)公式.与经典的晶体场理论(仅考虑中心金属离子的自旋-轨道耦合作用)相比较,该公式还包括了配体离子的自旋-轨道耦合作用的贡献,这一模型在应用于计算共价性较强的晶体光谱和电子顺磁共振谱可得到合理的结果.作为验证,用完全对角化方法研究了品体NiX2(X=Cl,Br,I)的光谱和电子顺磁共振谱,结果表明,理论与实验很好地符合.建立的全组态谱能级和电子顺磁共振公式为更精确地计算光谱和电子顺磁共振谱提供了一条可行方法.     

Optical spectrum, local lattice structure and EPR g factors for Cr impurity ions in MgTiO3 and LiTaO3

On the basis of the 120×120 complete energy matrices for a d³ configuration ion in a trigonal ligand field, for Cr³⁺ ions doped in MgTiO₃ and LiTaO₃, the local structures and EPR g factors of the octahedral (CrO₆)⁹⁻ clusters have been studied, respectively. By simulating the calculated optical spectra and the EPR spectra data to the experimental results, local structure parameters are obtained. The calculated results show that although the local lattice structures around the M (M=Mg²⁺, Ta⁵⁺) ions are obviously different, after Cr³⁺ replacing the M, the local lattice structures around the Cr³⁺ ions are quite similar and close to those of the Cr₂O₃. This may be ascribed to the fact that the octahedral Cr³⁺ center in MgTiO₃:Cr³⁺ and LiTaO₃:Cr³⁺ systems and that in Cr₂O₃ exhibit similar octahedral (CrO₆)⁹⁻ clusters. Moreover, the corresponding theoretical values of the optical spectra have been reported. It is also found that the orbital reduction factor k is very important to understand the EPR g factors for Cr³⁺ ions doped in MgTiO₃ and LiTaO₃.     

Variable temperature EPR spectra of Copper (II) ions in kainite crystals

X-band electron paramagnetic resonance (EPR) studies on divalent copper ions embedded in KMgClSO₄·3H₂O single crystals have been performed at low temperature (123 K). The angular variation of the EPR spectra reveals the presence of two Cu²⁺ sites, which have different orientations. The spin-Hamiltonian parameters of this six-coordinated cupric ion have been evaluated from the EPR spectra at 123 K. The forbidden lines due to Δm_I=±1 transitions are observed in between allowed transitions. The temperature variation EPR studies have also been performed both for a single crystal and a polycrystalline sample. The ground state wavefunction of Cu²⁺ ions has been estimated and is found to be an admixture of d_3z²−r² and d_x²−y². The temperature variation of the EPR spectra reveals that Cu²⁺ ions exhibit dynamic Jahn-Teller effect. From the polycrystalline EPR data, the temperature dependent magnetic susceptibilities are evaluated and discussed.     

Spin-spin and spin-other-orbit effects of optical spectra and the spin-Hamiltonian parameters for Cr ions in MgO crystals

An extended complete diagonalization method/microscopic spin-Hamiltonian (CDM/MSH) program has been developed, which is applicable for d³ ions at sites of tetragonal symmetry type I (C_4v, D_2d, D₄, D_4h) and trigonal symmetry type I (C_3v, D₃, D_3d). The Hamiltonian includes the spin-spin (SS) and spin-other-orbit (SOO) magnetic interactions besides the spin-orbit (SO) magnetic interaction usually taken into account. Utilizing the extended CDM/MSH program, the optical spectra, the spin-Hamiltonian (SH) parameters of the ground state ⁴B₁, and the splitting δ(²E) of the first excited ²E state for Cr³⁺ (3d³) ions at C_4v symmetry sites in MgO crystals have been successfully investigated. It is found that although the SO magnetic interaction is the most important one, the contributions to the SH parameters and the optical spectra from the SS and SOO magnetic interactions for Cr³⁺:MgO crystals are appreciable and should not be omitted, especially reaching 27.8% for the zero field splitting parameter D.     

Investigations of the electron paramagnetic resonance parameters and defect structures for Ni ions in CdX2 (X=Cl,Br) crystals

The high-order perturbation formulas of electron paramagnetic resonance (EPR) parameters (g factors g_∥,g_⊥ and zero-field splitting D) for 3d⁸ ions in trigonal octahedral clusters are established. These formulas contain the contributions not only from the crystal-field (CF) mechanism, but also from the charge-transfer (CT) mechanism (which is not considered in the widely used CF theory). From these formulas, the EPR parameters and the impurity-induced defect structures for Ni²⁺ ions in CdX₂ (X=Cl, Br) crystals are studied. The calculated EPR parameters are coincident with the experimental values, and the defect structure of Ni²⁺ impurity center obtained from the calculation is different from the corresponding structure in the host crystal. The sign of Q^CT (Q=Δg_∥, Δg_⊥, or D) due to CT mechanism agrees with that of the corresponding Q^CF due to CF mechanism and the relative importance of CT mechanism (characterized by Q^CT/Q^CF) increases with increasing covalence of 3d⁸ clusters and hence with raising atomic number of ligand X. So, in the explanations of the EPR parameters of 3d⁸ (or other 3dⁿ) ions in crystals with the heavy-element ligand ion (e.g., Br⁻), the calculated formulas based on the two-mechanism (CF and CT mechanisms) model are preferable to those based on only the CF mechanism in the CF theory.     

Theoretical studies of the optical and EPR spectra for V in Y2O3 crystal

In this paper, we give an alternative suggestion that both the observed optical and electron paramagnetic resonance (EPR) spectra of Yttrium oxide (Y₂O₃):V³⁺ are attributed to V³⁺ ions at the S₆ site of Y₂O₃. This suggestion is different from the opinion in the previous paper that the optical and EPR spectra are attributed to V³⁺ ions at the C₂ and S₆ sites, respectively. From the suggestion, the optical band positions and spin-Hamiltonian parameters are calculated by diagonalizing the complete energy matrix for 3d² ions in trigonal symmetry. The results are in good agreement with the experimental values, suggesting that both the observed optical and EPR spectra in Y₂O₃:V³⁺ may be due to V³⁺ at S₆ site of Y₂O₃ crystal.     

Spectral studies on Cu ions in sodium–lead borophosphate glasses

Electron Paramagnetic Resonance (EPR) and optical absorption spectra of Cu²⁺ ions in sodium–lead borophosphate glasses doped with different concentrations of Cu²⁺ ions have been studied. EPR spectra of all the glass samples exhibit resonance signals characteristic of Cu²⁺ ions. The values of spin-Hamiltonian parameters indicate that the Cu²⁺ ions in sodium–lead borophosphate glasses are present in octahedral sites with tetragonal distortion. The optical absorption spectra of all the glass samples show a single broad band, which has been assigned to the ²B_1g→²B_2g transition of Cu²⁺ ions. The optical band gap energy (E_opt) and Urbach energy (ΔE) are calculated from their ultraviolet absorption edges. The emission bands observed in the ultraviolet and blue region are attributed to 3d⁹4s→3d¹⁰ triplet transition in Cu⁺ ion. The FT-IR spectra show that the glass system contains BO₃, BO₄ and PO₄ structural units.     

EPR study of the impurity paramagnetic centres in (CaO−Ga2O3−GeO2) glasses

The X-band EPR spectra of Cr³⁺, Mn²⁺, and Fe³⁺ impurity ions in glasses of (CaO?Ga₂O₃?GeO₂) system are investigated in the 77÷300 K temperature range. The experimental data analysis yields the following results: (i) Impurity chromium ions are incorporated into the (CaO?Ga₂O₃?GeO₂) glasses network in Cr³⁺ (3d³,⁴F_3/2) paramagnetic valence state only and occupy the strong distorted oxygen coordinated octahedral sites. (ii) For all activated and non-activated (CaO?Ga₂O₃?GeO₂) glasses the iron impurity is present at concentration roughly 0.01 wt.%. Isotropic EPR signals atg _eff=4.29 andg _eff=2.00 are assigned to Fe³⁺ (3d⁵,⁶S_5/2) ions in the sites with strong rhombic distortion and in the sites with nearly cubic symmetry respectively. (iii) The manganese EPR spectrum in (CaO?Ga₂O₃?GeO₂) glasses is weakly dependent on temperature, doping procedure as well as manganese concentration. EPR spectra of impurity manganese ions in glasses with Ca₃Ga₂Ge₃O₁₂ and Ca₃Ga₂Ge₄O₁₄ compositions are virtually identical and belong to Mn²⁺ (3d⁵,⁶S_5/2) ions. Impurity manganese ions are incorporated into the (CaO?Ga₂O₃?GeO₂) glass network as isolated Mn²⁺ centres and clusters of Mn²⁺ ions.     

Theoretical investigation of the optical spectra and local lattice structure for Mn5+ in a Sr10(VO4)6F2 crystal

In this paper, the relationships between the optical spectra and local lattice structure for Mn⁵⁺ in a Sr₁₀(VO₄)₆F₂ crystal are established by the crystal- and ligand-field theory. The effect of spin–orbital coupling between the central 3d² ions and ligand ions has been considered in the full energy matrix. Using the matrix and superposition model formula, we have calculated the optical spectra and local lattice structure parameters of Mn⁵⁺ in Sr₁₀(VO₄)₆F₂ with a C_3v system. The calculated results are in good agreement with the observed values. In addition, the trigonal compressed distortions of the (MnO₄)^3? centers in Sr₁₀(VO₄)₆F₂ crystals are also obtained from the calculations.     

Local defect structures and EPR studies on (FeO6)9− and (FeO4)5− clusters in YGG: Fe3+ system

The octahedral (FeO₆)^9? and tetrahedral (FeO₄)^5? clusters in yttrium gallium garnet (YGG): Fe³⁺ system are investigated based on the 252 × 252 complete energy matrices for d⁵ configuration ions in trigonal and tetragonal ligand fields, moreover, the EPR and optical spectra are made unified calculation. The results indicate that the defect structures around Fe³⁺ centres display expansion effects at different temperatures 4.2 and 295 K, and which are close to those in YIG garnet, respectively. Simultaneously, the defect structure parameters for Fe³⁺ centres in YGG are determined, and the relationship between the defect structure and the temperature has been discussed.     

EPR, luminescence and IR studies of Mn activated ZnGa2O4 phosphor

Electron paramagnetic resonance (EPR), luminescence and infrared spectra of Mn²⁺ ions doped in zinc gallate (ZnGa₂O₄) powder phosphor have been studied. The EPR spectra have been recorded for zinc gallate phosphor doped with different concentrations of Mn²⁺ ions. The EPR spectra exhibit characteristic spectrum of Mn²⁺ ions (S=I=5/2) with a sextet hyperfine pattern, centered at g_eff=2.00. At higher concentrations of Mn²⁺ ions, the intensity of the resonance signals decreases. The number of spins participating in the resonance has been measured as a function of temperature and the activation energy (E_a) is calculated. The EPR spectra of ZnGa₂O₄: Mn²⁺ have been recorded at various temperatures. From the EPR data, the paramagnetic susceptibility (χ) at various temperatures, the Curie constant (C) and the Curie temperature (θ) have been evaluated. The emission spectrum of ZnGa₂O₄: Mn²⁺ (0.08 mol%) exhibits two bands centered at 468 and 502 nm. The band observed at 502 nm is attributed to ⁴T₁→⁶A₁ transition of Mn²⁺ ions. The band observed at 468 nm is attributed to the trap-state transitions. The excitation spectrum exhibits two bands centered at 228 and 280 nm. The strong band at 228 nm is attributed to host-lattice absorption and the weak band at 280 nm is attributed to the charge-transfer absorption or d⁵→d⁴s transition band. The observed bands in the FT-IR spectrum are assigned to the stretching vibrations of M-O groups at octahedral and tetrahedral sites.     

Electron paramagnetic resonance and photoluminescence of NaBi(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystals doped with gadolinium ions

The results of electron paramagnetic resonance (EPR) and photoluminescence studies of large NaBi(MoO₄)₂ crystals grown by the low-gradient Czochralski method and doped with gadolinium ions (0.1 wt %) have been presented. It has been found from the analysis of the angular dependence of EPR spectra that the gadolinium ions enter into the crystal structure in the state Gd³⁺ and occupy the bismuth position. The parameters of the EPR spectra of the gadolinium ions have been calculated and the analogy has been drawn based on these data between the specific features of the incorporation of gadolinium ions into the structures of double tungstates and molybdates. The observed shift of the maximum of the photoluminescence band of the NaBi(MoO₄)₂ crystals doped with Gd³⁺ ions with respect to the spectrum of the undoped crystal suggests the influence of gadolinium ions on the formation of the bottom of the conduction band caused by the states of the (MoO₄)^2?.     

EPR and optical absorption studies on VO ions in KZnClSO4·3H2O single crystals—an observation of superhyperfine structure

EPR spectra of VO²⁺ ions doped in KZnClSO₄·3H₂O single crystals have been studied at different temperatures. The EPR spectrum shows a well-resolved hyperfine and superhyperfine structure patterns. The angular variation of EPR spectra reveals the presence of more than three magnetic complexes, which correspond to distinct sites of VO²⁺ ion. From the angular variation EPR data, the spin-Hamiltonian parameters are evaluated and discussed. The optical absorption spectrum studied at room temperature shows bands corresponding to C_4v symmetry. From the EPR and optical data, the molecular-orbital bonding coefficient ε² and β² are evaluated and discussed. The observed five-line superhyperfine structure has been attributed to four protons (with I=1/2) from the surrounding water molecules of one of the vanadyl sites.     

Investigations of the g factors for the trigonal [Ti(H2O)6] clusters in frozen solution from two microscopic spin Hamiltonian methods

The spin Hamiltonian parameters (SH) (g factors g_∥ and g_⊥) for the trigonal [Ti(H₂O)₆]³⁺ clusters in the rapidly frozen solutions of Ti³⁺ are calculated from the complete diagonalization (of energy matrix) method (CDM, which is established in this paper) and the perturbation theory method (PTM). The two methods are based on the two-spin-orbit-parameter model (where both the contribution due to the spin-orbit (SO) coupling parameter of central 3dⁿ ion and that of ligand are included) rather than the one-SO-parameter model in the conventional crystal-field theory (where only the contribution due to the SO coupling parameter of 3dⁿ ion is considered). The calculated results from both methods are not only consistent with the observed values, but also close to each other. This suggests that both methods can be effective in the studies of SH parameters.     

Synthesis, crystal structure, Cu doped EPR and voltammetric studies of bis[N-(2-hydroxyethyl)ethylenediamine]zinc(II) squarate monohydrate

Crystal structure of [Zn(hydet-en)₂]·C₄O₄·H₂O (ZHES) (hydet-en is N-(2-hydroxyethyl)ethylenediamine) complex has been synthesized and characterized by analytical, spectroscopic (IR, UV/Vis) and voltammetric techniques. After doping Cu²⁺ ion, its magnetic environment has been identified by electron paramagnetic resonance (EPR) technique. The title complex crystalizes in monoclinic system with space group P2₁/c and with Z=4. Each hydet-en ligand acts as a tridentate ligand through the two N atoms and the hydroxyl O atom, resulting in a six coordinate Zn(II) ion. The EPR spectra were recorded in three perpendicular planes of Cu²⁺ doped ZHES single crystal. The calculated g and A values indicated that the paramagnetic center is rhombic symmetry with the Cu²⁺ ion having distorted octahedral environment. The molecular orbital bond coefficients of the Cu(II) ion in d⁹ state is also calculated by using EPR and optical absorption parameters. The dianion SQ²⁻ is oxidized reversibly in two consecutive steps to the corresponding radical monoanion and neutral form.     

Nature of optical properties of GdFe3(BO3)4 and GdFe2.1Ga0.9(BO3)4 crystals and other 3d5 antiferromagnets

Influence of the partial substitution of paramagnetic Fe³⁺ ions by diamagnetic Ga³⁺ ions in the trigonal crystal GdFe₃ (BO₃)₄ on its optical and magnetic properties is studied and discussed in connection with problems common for all antiferromagnets containing 3d ⁵ ions. Polarized optical absorption spectra and linear birefringence of GdFe₃ (BO₃)₄ and GdFe_2.1Ga_0.9 (BO₃)₄ single crystals have been measured in the temperature range 85–293 K. Specific heat temperature dependence (2–300 K) and structure of GdFe_2.1Ga_0.9 (BO₃)₄ crystal have been also studied. As a result of substitution of 30% Fe to Ga the Neel temperature diminishes from 38 till 16 K, the strong absorption band edge shifts on 860 cm^-1 (0.11 eV) to higher energy and the d-d transitions intensity decreases substantially larger than the Fe concentration does. Strong absorption band edge is shown to be due to Mott-Hubbard transitions. Correlation between position of the strong absorption band edge and the Neel temperature of antiferromagnets has been revealed. Properties of the doubly forbidden d-d transitions in the studied crystals and in other antiferromagnets are explained within the framework of the model of the exchange-vibronic pair absorption, which is theoretically analyzed in detail. The model permitted us to determine the connection between parameters of d-d absorption bands (intensity, width and their temperature dependences), on the one hand, and the exchange, spin-orbit and electron-lattice interactions, on the other hand.     

Electron paramagnetic resonance of scandium in silicon carbide

The EPR spectra of scandium acceptors and Sc²⁺(3d) ions are observed in 6H-SiC crystals containing a scandium impurity. The EPR spectra of scandium acceptors are characterized by comparatively small hyperfine interaction constants, whose values are consistent with the constants for other group III elements in SiC: boron, aluminum, and gallium acceptors. The EPR spectra of scandium acceptors undergo major changes in the temperature interval 20–30 K. In the low-temperature phase the EPR spectra are characterized by orthorhombic symmetry, whereas the high-temperature phase has higher axial symmetry. The EPR spectra observed at temperatures above 35 K and ascribed by the authors to Sc²⁺(3d) ions, or to the A ²⁻ state of scandium, have significantly larger hyperfine structure constants and narrower lines in comparison with the EPR spectra of scandium acceptors. The parameters of these EPR spectra are close to those of Sc²⁺(3d) in ionic crystals and ZnS, whereas the parameters of the EPR spectra of scandium acceptors correspond more closely to the parameters of holes localized at group III atoms, in particular, at scandium atoms in GeO₂. It is concluded that in all centers the scandium atoms occupy silicon sites. Fiz. Tverd. Tela (St. Petersburg) 39, 52–57 (January 1997)     

EPR and optical absorption studies of Fe ions in sodium borophosphate glasses

Electron paramagnetic resonance (EPR) and optical absorption spectral investigations have been carried out on Fe³⁺ ions doped sodium borophosphate glasses (NaH₂PO₄-B₂O₃-Fe₂O₃). The EPR spectra exhibit resonance signals with effective g values at g=2.02, g=4.2 and g=6.4. The resonance signal at g=4.2 is due to isolated Fe³⁺ ions in site with rhombic symmetry whereas the g=2.02 resonance is due to Fe³⁺ ions coupled by exchange interaction in a distorted octahedral environment. The EPR spectra at different temperatures (123-295 K) have also been studied. The intensity of the resonance signals decreases with increase in temperature whereas linewidth is found to be independent of temperature. The paramagnetic susceptibility (χ) was calculated from the EPR data at various temperatures and the Curie constant (C) and paramagnetic Curie temperature (θ_p) have been evaluated from the 1/χ versus T graph. The optical absorption spectrum exhibits bands characteristic of Fe³⁺ ions in octahedral symmetry. The crystal field parameter (Dq) and the Racah interelectronic repulsion parameters (B and C) have also been evaluated and discussed.     

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.     

EPR and optical investigation of VO(II) in Zn(C3H3O4)2(H2O)2 single crystals: An interstitial site

EPR spectroscopic investigations on single crystals of diaquabis[malonato(1-)-κ²O,O′] zinc(II) doped with VO(II) ion have been carried out at X-band frequencies and at 300 K. The single crystal, rotated along the three mutually orthogonally axes, has yielded spin-Hamiltonian parameters g and A as: g_xx=1.980, g_yy=1.972, g_zz=1.937 and A_xx=8.4, A_yy=6.1, A_zz=18.1 mT, respectively. These spin-Hamiltonian parameters reflect a slight deviation from axial symmetry to rhombic, which is elucidated by the interstitial occupation of vanadyl ions. The isofrequency plots and powder EPR spectrum have been simulated. The percentage of metal-oxygen bond has been estimated. The optical absorption spectrum exhibits four bands at 257, 592, 720 and 764 nm suggesting a C_4v symmetry. The admixture coefficients and bonding parameters have also been calculated by collaborating EPR data with optical data.