三角畸变立方晶场中d2离子的零场分裂与劈裂因子

用不可约张量方法,利用由广义Winier-Eckart定理得出的两个推论及有关结果,对三角畸变立方晶场中的d²离子,考虑到V_c及(V_t+H_s)产生的所有可能的相互作用,并用缩小因子来计入共价键与J-T效应,通过逐级微扰求得基态波函数,从而导出了g_∥, g_⊥与D的公式。应用于钒刚玉,通过全面拟合光谱与g_∥, g_⊥,D实验值,得到的结果与实验值较好的符合。对所用模型、方法、结果与考虑所有相互作用的重要性等问题作了讨论。 关键词：     

铜化合物ESR g张量和A张量的相关性及其与结构的关系

对于某些含有特定配位原子的钢化合物,找出了钢的ESR g_‖和A_‖之间的线性相关性;总结了相关性与钢化合物的分子结构间的联系;认为相关性与分子对称性及分子轨道性有关,分子对称性的提高和钢-配体间成键分子轨道共价性的降低引起g_‖的增大和A_‖绝对值的减小,对某些钢化合物,g_‖与β₁²,A_‖与β₁²之间存在线性关系.总结出由实测的g_‖和A_‖估算分子轨道系数β₁²值的方法.     

四角或三角畸变立方晶场中(3d)1过渡金属离子的劈裂因子

对四角或三角畸变立方晶场中的(3d)¹离子,在已有的静电晶场理论的基础上,采用“集团模型”,进一步引入Γ_∥, Γ_⊥及K_∥, K_⊥,R_∥, R_⊥,并考虑E_g混入T_2g,导出适用于四角或三角畸变立方晶场各种可能情况的g_∥, g_⊥公式。讨论了g_∥, g 关键词：     

Mo-SiO2-C3H6催化反应体系的ESR动态表征

文章考察了Mo-SiO₂催化剂体系在丙烯歧化反应过程中的动态ESR波谱,发现在催化歧化反应过程中有两种Mo⁵⁺顺磁中心,一种为扰动八面体配位,g_||=1.89,g_⊥=1.94;另一种为扰动四棱锥配位,g_||=1.86,g_⊥=1.95。测得同位素^95,97Mo⁵⁺的各向异性超精细耦合常数A_||=90.3×10^-4cm^-1,A_⊥=44.8×10^-4cm^-1;观测到反应产生的积炭信号,g≈2.0O₂;氧阴离子自由基信号g₁=2.018,g₂=2.011,g₃=2.005。用LCAO-MO理论对上述Mo⁵⁺的ESR波谱进行计算,求得分子轨道系数,发现并总结出△g_||/△g_⊥与△g成直线关系,并建议用△g_||/△g_⊥=4(△E(B₂→E))/(△E(B₂→B₁)(β₁/ε)²之比值作为衡量C_4v扰动程度的尺度。     

α-Al2O3单晶中Fe3+离子的电子顺磁共振

本文对α-Al₂O₃单晶体中Fe³⁺离子在室温下,X波段进行了电子顺磁共振研究,发现Fe³⁺离子实际上占据四种磁性不等价晶位。在同一氧离子层间的两种晶位上的Fe³⁺离子具有相同的自旋哈密顿参量,而不同氧离子层间的晶位上的Fe³⁺离子具有不同的自旋哈密顿参量,两种自旋哈密顿参量为:(1)g_‖=2.001,g_⊥=2.003,D=1679 关键词：     

五种还原Keggin结构杂多阴离子的ESR谱

本文报道了五种具有Keggin结构的还原杂多阴离子的溶液和-150℃冷冻ESR谱,它们是SiV₂Mo₁₀O₄₀^6-、bSiV₂Mo₉O₄₀^7--、PV₃Mo₉O₄₀^6-、PV₃W₉O₄₀^6-和VV₃W₉O₄₀^6-。在室温下pH≤3时,所有杂多酸阴离子均为8条锐线,pH=7-8时,均为8+15条线并且随着放置时间增长逐步变成8条线。在-150℃时均呈现出V⁴⁺8条线的复杂粉末谱,作者根据一种修正的Ble-aney方法成功地模拟了这些冷冻谱,得出g_‖、g_⊥、A_‖、A_⊥,按照DeArmond理论计算了近似的K、α值并讨论了它们的物理意义。最后从异构体的数目和简并度的观点初步解释了观察不到V₃物种22条超精细线的原因。Back     

三角对称晶场下d8电子组态的EPR参量的普遍公式及其应用

本文考虑到d⁸电子组态中所有自旋三重态和自旋单态对基态的影响,用高阶微扰法导出了d⁸电子组态在三角对称晶场下光谱和基态EPR普遍公式。发现在三角对称晶场下,d⁸电子组态离子的g_⊥ > g_‖或g_⊥ < g_‖和D > 0或D < 0是以立方对称晶场为界,晶体中顺磁离子的配体沿C₃轴伸长或压缩所致。利用所得公式计算了NiCl₂和NiSiF₆·6H₂O晶体的EPR参量,其结果与实验吻合较好。     

三角畸变立方晶场中d~2离子的吸收光谱

用不可约张量方法,由广义Wigner-Eckart定理得出两个推论及有关结果。对三角畸变立方晶场中的d~2离子,提出了从统一模型出发,计入V_c及(V_(tr) H_s)产生的所有可能的相互作用,全面处理光谱与D,g_∥,g_⊥问题的有效方法。 应用于钒刚玉,通过全面拟合光谱与D,g_∥,g_⊥实验值,得到的结果与实验值满意地符合。 对所用的模型、方法等问题进行了讨论。     

掺杂聚乙炔中的孤子振动定域模

在SSH模型基础上,本文研究了掺杂聚乙炔链中杂质势对孤子振动模的束缚影响。不同边界条件下的数值计算发现Goldstone模将受到杂质钉扎并出现两个新的定域模g₁′和g₂′。另外,还得到了其它已知的定域模g₂,g₃和g₅,这些定域模随杂质势的敏感程度各有不同,在所取参数下取得了与实验基本一致的结果。 关键词：     

KMgF3:Cr3+的EPR参量和K+空位研究

EPR和ENDOR表明:顺磁离子取代KMgF₃中的Mg²⁺离子后,所处的环境具有轴对称。本文研究了KMgF₃:Cr³⁺的Δg=g_∥-g_⊥和零场分裂值D,证实KMgF₃:Cr³⁺中K⁺空位的存在。并且指出:由于K⁺空位,使Cr³⁺的最近邻F^-离子分 关键词：     

On the <Emphasis Type="Italic">g</Emphasis>-factor value of canted antiferromagnet CoCO<Subscript>3</Subscript>

Experimental data on the magnetization of canted antiferromagnet CoCO₃ (T_N = 18.1 K) in the paramagnetic region are described by the isotropic g factor g_‖ = g_⊥ = 6.5 that differs from the anisotropic values g_‖ = 3.05 and g_⊥ = 4.95 obtained in electron paramagnetic resonance (EPR) measurements at T = 4.2 K on Co²⁺ ions in magnetically diluted crystals. The g-factor values calculated in the Abragam-Pryce and Weiss molecular field approximations using the magnetization data in the magnetic ordered region correspond to data obtained in EPR measurements. It is shown that the absence of the anisotropy of the g factor at high temperatures cannot be explained in the approximations used. Causes of the observed discrepancies are discussed.     

Intrinsic V- and Vo centers in single crystal SrO

The intrinsic V^- center (a positive hole trapped at a cation vacancy) has been observed in single crystals of SrO following x-irradiation at 77 K. The ESR spectrum corresponds to a spin-$\text{1}\text{2}$ defect having <100> axial symmetry with g₆ = 2.0012(3) and g_⊥ = 2.0703(3). The concentration of V^- centers was enhanced significantly by heating crystals in oxygen at 1000°C and rapidly quenching. V^o centers (two holes trapped at a cation vacancy) were also observed after x-irradiation at low temperature, with g₆ = 2.0011(3), g_⊥ =2.0751(3), and D = 380.4(5) MHz.     

Electron-nuclear-double-resonance of the VAl center in MgO

An ENDOR study of a hole center in MgO with g_|=2.0032±0.0001 and g_⊥=2.0385±0.0001 reveals that the hole interacts with an axial aluminum ion with A_⊥=±0.178±0.008 MHz, A_⊥=±0.074±0.008 MHz, and P= ±0.366±0.002 MHz. The structure of the center is consistent with the label, V_Al. It is suggested that the V_Al center may have been mistaken in the past for the V^- center because of the similarity of their g-values, method of production, and thermal properties.     

Electron paramagnetic resonance of Dy3+ ions in lead thiogallate single crystals

The results of electron paramagnetic resonance (EPR) studies of Dy³⁺ ions in lead thiogallate PbGa₂S₄ single crystals have been presented. It has been shown that the ground state of these ions corresponds to the lowest Stark sublevel Γ₆ of the term ⁶ H _15/2. The spectra are well described by the axially symmetric spin Hamiltonian with the effective spin S = 1/2 with the factors g _‖ = 15.06 and g _⊥ = 2.47. The Dy³⁺ ions substitute Pb²⁺ ions in the crystal lattice of PbGa₂S₄. The observed hyperfine structure has allowed to unambiguously interpret the EPR spectra. The hyperfine interaction constants of two odd isotopes of dysprosium in lead thiogallate single crystals have been found to be A _‖ = 675 × 10^?4 cm^?1 and A _⊥ = 111 × 10^?4 cm^?1 for ¹⁶³Dy and A _‖ = 472 × 10^?4 cm^?1 and A _⊥ = 77 × 10^?4 cm^?1 for ¹⁶¹Dy.     

Electron spin relaxation studies of La@C82 in the solid state by EPR

The temperature dependence of EPR spectrum of La@C₈₂ in the powder of empty C₆₀ and C₇₀ mixed crystals was studied by EPR spectroscopy employing X- and Q-band microwave frequencies. The rigid limit spectra (at 4.2 K for the X-band and at 132 K for the Q-band) could be analyzed by static spectral simulation which yielded the EPR parameters,g _‖=2.0021,g _⊥=1.9970,^La A _⊥=7.8 MHz,^La A _‖～0 MHz and an isotropic¹³C coupling value of about 3 MHz. For higher temperatures an appreciable motional averaging effect was observed and the spectra were analyzed by using dynamic spectral simulation based on the stochastic Liouville equation, where we assumed an isotropic rotational motion with the Brownian diffusion. The calculated spectra reproduced the dominant feature of the temperature dependence of the spectra almost satisfactorily for both the X-and Q-band frequencies with the appropriate rotational correlation times. The Arrhenius plots of the correlation time gave two activation energies of 0.9 kcal/mol and 2.9–3.8 kcal/mol for the temperatures below and above 200 K, respectively.     

Local structure of the trigonal defect center for Cr3+ ions in KMgF3 crystals

Abstract

The zero-field splitting D, the anisotropic g-factors g _∥, Δg(=g _∥ ? g _⊥) and the first excited state splitting Δ(² E) for the trigonal Cr³⁺–V_K center in KMgF₃: Cr³⁺ crystals have been studied from Macfarlane's high-order perturbation formulas. From the studies, the local structure of the trigonal center is obtained. The local lattice distortions (i.e., the displacement directions of the ions in the center) are consistent with the expectation based on the electrostatic interaction.     

Theoretical explanation of absorption spectra and ESR parameters of Cu in shattuckite

The optical absorption spectra and electronic spin resonance parameters (ESR g factors g_‖, g_⊥ and hyperfine structure constants A_‖, A_⊥) for Cu²⁺ in shattuckite crystal are calculated from the two spin–orbital coupling parameters model, high-order perturbation formulas and complete diagonalization (of energy matrix) method (CDM) of 3d⁹ ion in tetragonal symmetry. The calculated results are in good agreement with the observed values. Since the ESR parameters are sensitive to the local structure of a paramagnetic impurity center, the defect structure of Cu²⁺ center in shattuckite crystal is estimated. The results are discussed.     

EPR parameters and local lattice structure study of V ions in CdCl2 and CsMgCl3 crystals

The local lattice structure and EPR parameters (D, g_‖, g_⊥) have been studied systematically on the basis of the complete energy matrix for a d³ configuration ion in a trigonal ligand field. By simulating the calculated optical and EPR spectra data to the experimental results, the local distortion parameters (ΔR, Δθ) are determined for V²⁺ ions in CdCl₂ and CsMgCl₃ crystals, respectively. The results show that the local lattice structure of CdCl₂:V²⁺ system exhibits a compression distortion (ΔR=−0.0868 Å) while that of CsMgCl₃:V²⁺ system exists an elongation distortion (ΔR=0.0165 Å). The different distortion may be ascribed to the fact that the radius of V²⁺ ion is smaller than that of Cd²⁺ ion or larger than that of Mg²⁺ ion. Moreover, the relationships between EPR parameter D and local structure parameters (R, θ) as well as the orbital reduction factor k and g‐factors (g_‖, g_⊥) are discussed.