Investigations of the optical spectra and spin-Hamiltonian parameters for the rhombic Yb centers in garnets

Two complete diagonalization (of energy matrix) methods (CDM-I and CDM-II) are used to calculate the six optical spectral band positions and nine spin-Hamiltonian (SH) parameters (g factors g_i and hyperfine structure constants ¹⁷¹A_i, ¹⁷³A_i, where i=x, y, z) for Yb³⁺ ions in the rhombic dodecahedral sites of garnets Y₃Al₅O₁₂, Lu₃Al₅O₁₂ and Y₃Ga₅O₁₂. In CDM-I, the Hamiltonian concerning energy matrix does not contain the Zeeman and hyperfine interaction terms, whereas in CDM-II, it does. So, in CDM-I, the SH parameters are obtained by first-order perturbation method or the equivalence between SH and Zeeman term (or hyperfine interaction term) and in CDM-II, the SH parameters and optical spectral band positions are calculated together. The results obtained from both methods are not only close to each other, but also in reasonable agreement with the observed values. So the second-order perturbation formulas of SH parameters developed recently are incorrect and unnecessary.     

CuAlS2：Ni^＋晶体光谱和电子顺磁共振谱研究

Ni^＋离子在三元化合物CuAlS2半导体中替代离子Cu^＋。应用晶体场理论，结合CuAlS2中Cu^＋位置的结构数据，计算了CuAlS：Ni^＋晶体的光谱和电子顺磁共振谱（g因子和超精细结构常数），计算结果与实验值符合得很好。     

Theoretical studies of the optical and EPR spectra for vanadyl ions in alkaline-earth aluminoborate glasses

The optical spectra and electron paramagnetic resonance (EPR) g and A factors of calcium aluminoborate glasses (CaAB) : VO²⁺ are calculated using a complete diagonalization (of the energy matrix) process (CDP). Good agreement between the theoretical values and experimental results indicates the effectiveness of the CDP method for theoretical studies of optical and EPR spectra of 3d¹ (or V⁴⁺) ions in glasses.     

CuAlS2∶Ni+晶体光谱和电子顺磁共振谱研究

Ni 离子在三元化合物CuAlS2半导体中替代离子Cu .应用晶体场理论,结合CuAlS2中Cu 位置的结构数据,计算了CuAlS2∶Ni 晶体的光谱和电子顺磁共振谱(g因子和超精细结构常数),计算结果与实验值符合得很好.     

Theoretical investigation of optical and EPR spectra for nickel (II) in ANSH crystal

Based on the semi-self-consistent field (semi-SCF) d-orbital theory and point charge model, we have studied the optical spectra by the complete diagonalizing (of energy matrix) method (CDM) and electronic paramagnetic resonance (EPR) spectra by the perturbation theory method (PTM) for Ni²⁺ center in the ammonium nickel(II) sulfate hexahydrate [(NH₄)₂Ni(SO₄)·6H₂O, abbr. ANSH] crystal. The structural parameters of the ANSH crystal have been obtained and theoretical results agree well with the experimental findings.     

Theoretical calculations of the optical band positions and spin-Hamiltonian parameters for Yb at the tetragonal Y site of KY3F10 crystal

The six optical band positions and six spin-Hamiltonian parameters [g factors g_∥, g_⊥ and hyperfine structure constants A_∥(¹⁷¹Yb³⁺), A_⊥(¹⁷¹Yb³⁺), A_∥(¹⁷³Yb³⁺), A_⊥(¹⁷³Yb³⁺)] for Yb³⁺ ion at the tetragonal Y³⁺ site of KY₃F₁₀ crystal are calculated from a diagonalization (of energy matrix) method. In the method, the Hamiltonian of energy matrix contains the free-ion, crystal-field interaction, Zeeman (or magnetic) interaction and hyperfine interaction terms and so a 14×14 complete energy matrix for 4f¹³ ion in tetragonal crystal-field and under an external magnetic field is constructed. Diagonalizing the energy matrix, these optical and EPR spectral data are calculated together and the calculated results are in reasonable agreement with the experimental values. The signs of hyperfine structure constants A_∥, A_⊥ for the isotopes ¹⁷¹Yb³⁺ and ¹⁷³Yb³⁺ in KY₃F₁₀ are suggested. The results are discussed.     

Theoretical investigation of the optical spectra and g factors for Cu2+ in dioptase

The optical spectra of Cu²⁺ in dioptase are calculated using crystal-field theory. Good agreement between measured and calculated energy values is obtained under D _4h point-symmetry approximation. The electron paramagnetic resonance g factors, g _// and g _⊥, are also investigated from high-order perturbation formulae. The local structure of Cu²⁺ in dioptase is obtained using these formulae. Theoretical results are in perfect agreement with experimental findings.     

Characterization of red sandalwood by ICP-MS analysis,optical absorption and EPR spectroscopic methods

Red sandalwood sample was subjected to ICP-mass spectrometer analysis for the determination of minor elements. The ash of the sample was also analysed for the presence of major elements. The minor elements present include Cu (281.256), Ba (3722.064), Sr (6365.482), Rb (45.285), Ce (49.863), Zn (375.433) and Pb (80.944) all in ppt. The major elements detected are Cd, Fe, Mn and Ni. Optical absorption spectrum indicates that Fe(III) and Ni(II) are in tetragonal distortion with octahedral geo-metry. ESR (electron spin resonance) spectral analysis also confirms Fe(III) in tetragonal distortion, and the g-values observed for Fe(III) are 6.52, 2.63 and 1.92 and for Mn(II) is 1.99. NIR spectrum is due to carbonate overtones and harmonics and water fundamentals.     

Theoretical study of the dependence of EPR spectra on local structure for octahedral Cr3+ centres in oxides and fluorides series

A theoretical method for investigating the inter-relation between the EPR parameters and local structure has been established on the basis of the complete energy matrices for 3d³ configuration ions in both the trigonal and tetragonal ligand fields. By means of this method, the local structure of the octahedral Cr³⁺ centres in double molybdates series and spinels series as well as the perovskite-type fluorides series has been studied systematically. Furthermore, the dependence of the EPR zero-field splitting parameter D on the local structure parameters in both trigonal and tetragonal ligand-fields has been revealed, simultaneously. The inter-relation between the EPR parameters D and Δg(g _// ??g _⊥) is also elucidated.     

不对称双席夫碱过渡金属配合物的电子光谱和非线性光学性质的理论研究

本文采用密度泛函理论中的M05方法对比研究了一类双席夫碱及其衍生物与金属Co、Ni和Cu配位后配合物的结构,非线性光学性质以及激发态性质.结果表明,Co配合物的三重态,Ni配合物的二重态以及Cu配合物的单重态为最佳稳定结构.通过最佳稳定结构计算得到的配合物非线性光学性质表明,三种金属配合物中Cu配合物表现出较高的一阶和二阶超极化率.通过对其激发态性质分析表明在配体苯环上引入甲氧基使电子跃迁种类减少,导致超极化率下降,非线性光学性质减弱.     

不对称双席夫碱过渡金属配合物的电子光谱和非线性光学性质的 理论研究

本文采用密度泛函理论中的M05方法对比研究了一类双席夫碱及其衍生物与金属Co、Ni和Cu配位后配合物的结构,非线性光学性质以及激发态性质. 结果表明,Co配合物的三重态,Ni配合物的二重态以及Cu配合物的单重态为最佳稳定结构. 通过最佳稳定结构计算得到的配合物非线性光学性质表明,三种金属配合物中Cu配合物表现出较高的一阶和二阶超极化率. 通过对其激发态性质分析表明在配体苯环上引入甲氧基使电子跃迁种类减少,导致超极化率下降,非线性光学性质减弱.     

Theoretical studies of the spin-Hamiltonian parameters for the orthorhombic Pr4+ centers in Sr2CeO4 crystals

Theoretical studies of spin-Hamiltonian (SH) parameters associated with Pr⁴⁺ in Sr₂CeO₄ single crystals have been made by using the complete diagonalizing energy matrix method (CDM) for the 4f ¹ electronic configuration. The calculated results are in excellent agreement with the experimental data. The negative signs of the anisotropic g _i -factors and hyperfine structure constants A _i (where i = ∥ or ⊥) for the orthorhombic Pr⁴⁺ ion in Sr₂CeO₄ are suggested from the calculations. By comparing the results obtained by the CDM with the experimental data, one finds it is valid to interpret the SH parameters for 4f ¹ ions in crystals. The results are discussed.      

ZnO:V3+晶体光谱和电子顺磁共振谱的理论研究

采用强场耦合图像,建立了3d2电子组态在三角对称中的45×45能量矩阵,通过对角化完全能量矩阵的方法,计算出了ZnO:V3 晶体的45条光谱能级和5个电子顺磁共振谱参量(零场分裂D,g因子g//,g⊥和超精细结构常数A//,A⊥),计算结果与实验数值能很好地符合.计算中还发现V3 杂质中心的局部结构与基质晶体的结构不一致,即V3 在ZnO中并不占据准确的Zn2 位置,而是沿c3轴方向位移一段距离△Z≈0.003 nm.作者对上述这些结果的合理性进行了讨论.     

The optical and paramagnetic absorption spectra of MgO:Mn single crystals irradiated in a reactor

The optical and paramagnetic absorption spectra of MgO:Mn crystals of different origin, irradiated in a reactor, have been investigated. It is found that, in spite of only a small amount of Mn²⁺ impurity ions in the investigated crystals, their influence on the efficiency of formation and accumulation of F⁺-centers is dominant. The dependence of the number of F⁺-centers both on irradiation dose and on manganese concentration is studied.     

Theoretical investigation of the spin-Hamiltonian parameters and optical spectra for the doped Cu2+ in ZnCdO nanopowder

The spin-Hamiltonian (SH) parameters (g factors g_||, g_⊥ and hyperfine structure constants A_||, A_⊥) and d–d transitions for ZnCdO:Cu²⁺ are calculated based on the perturbation formulas for a 3d⁹ ion in tetragonally elongated octahedra. Good agreement between the calculated results (four SH parameters and three optical absorption bands) and the experimental results can be obtained. Since the SH parameters are sensitive to the local structure of a paramagnetic impurity center, the tetragonal distortion (characterized by the relative elongation ratio ρ ≈ 3.5% along the C₄ axis) of the impurity center due to the Jahn–Teller effect is also acquired from the calculations. The negative and positive signs of hyperfine structure constants A_|| and A_⊥ for ZnCdO:Cu²⁺, respectively, are also suggested in the discussions.     

Theoretical studies of the optical and EPR spectra for Fe ion in the MF3:Fe (M=Al, Ga) systems

By analyzing the EPR spectra of Fe³⁺ ion in the fluorinde glasses, the local lattice structures around impurity Fe³⁺ ion in MF₃:Fe³⁺ (M=Al, Ga) systems have been studied by means of diagonalizing the complete energy matrices of the electron-electron repulsion, the ligand-field and the spin-orbit coupling for a d⁵ configuration ion in a trigonal ligand-field. Both the second-order and fourth-order EPR parameters D and (a−F) are taken simultaneously in the structural investigation. The results indicate that the local lattice structure around octahedral Fe³⁺ center has an expansion distortion for Fe³⁺ in MF₃:Fe³⁺ (M=Al, Ga). The expansion distortion may be ascribed to the fact that the radius of Fe³⁺ ion is larger than that of Al³⁺ ion and Ga³⁺ ion, and the Fe³⁺ ion will push the fluoride ligands upwards and downwards, respectively. The local lattice structure parameters R=1.927 A, θ=55.538° for Fe³⁺ in AlF₃:Fe³⁺ and R=1.931 A, θ=56.09° for Fe³⁺ in GaF₃:Fe³⁺ are determined, respectively, and the EPR spectra of the MF₃:Fe³⁺ (M=Al, Ga) systems are satisfactorily explained.