Electron paramagnetic resonance study of Fe<Superscript>3+</Superscript> ions at octahedral and tetrahedral mirror symmetry sites in the LiScGeO<Subscript>4</Subscript> crystal

An electron paramagnetic resonance (EPR) study of a synthetic single crystal of LiScGeO₄ doped with Cr ions carried out earlier at the X- and Q-bands at 300, K has indicated additional weak lines. A detailed analysis of these EPR lines, which were tentatively attributed to the Fe³⁺ ions at two different mirror symmetry sites, is presented in this paper. The angular dependences in the three crystallographic planes were resolved by fitting the two distinct spectra denoted Fe³⁺(I) and Fe³⁺(II) with a spin Hamiltonian (S=5/2) of monoclinic symmetry. The rank-4 crystal field tensors at tetrahedral and octahedral sites were calculated with the point-charge model to determine the principal axis orientations of their cubic, tetragonal and trigonal components. A comparative analysis of the zero-field splitting tensors and the crystal field ones indicates that Fe³⁺(I) ions substitute for Sc³⁺ at octahedral sites and Fe³⁺(II) ions substitute for Ge⁴⁺ at tetrahedral sites with no significant distorition of the coordination polyhedra in the structure of LiScGeO₄.     

EPR, optical absorption and superposition model study of Fe³(+) doped strontium nitrate single crystals

Electron paramagnetic resonance (EPR) study of Fe3(+) ions doped strontium nitrate (SN) single crystals is performed at liquid nitrogen temperature and at X band frequency. The spin Hamiltonian (SH) parameters are determined from the resonance lines observed at different angular rotations. The crystal field parameters (CFPs) are evaluated using superposition model of Newman. The Zeeman g-factor and zero-field splitting parameters (ZFSPs) of Fe3(+) ion in SN (truncated SH considered) are: g=1.9989 ± 0.002 and ∣D∣=(338 ± 5) × 10?? cm?1, ∣E∣=(10 ± 5)× 10?? cm?1, a=(458 ± 5)× 10?? cm?1, respectively. The Fe3(+) ion enters the lattice substitutionally replacing the Sr2(+) sites of cubic symmetry. The local site symmetry of Fe3(+) ion in the crystal is orthorhombic (lower than that of the host). The optical absorption study of the crystal is also done at room temperature in the wavelength range 195-925 nm. The energy values of different orbital levels are determined. The observed bands are assigned as transitions from the (6)A?(g)(S) ground state to various excited states of Fe3(+) ion in a cubic crystal field approximation. The observed band positions are fitted with four parameters, the Racah interelectronic repulsion parameters (B and C), the cubic crystal field splitting parameter (Dq) and the Trees correction (α) yielding: B=934, C=2059, Dq=1450, and α=90 (in cm?1). On the basis of EPR and optical data, the nature of metal-ligand bonding in this crystal is discussed. The ZFSPs are also determined theoretically using microscopic SH theory based on perturbation theory and CFPs, B(kq) obtained from superposition model. The values of ZFSPs thus obtained are ∣D∣=(340 ± 5) × 10?? cm?1 and ∣E∣=(15 ± 5) × 10?? cm?1.     

EPR,optical absorption and superposition model studies of Fe3+-doped cesium chloride single crystals: a case of substitutional as well as interstitial sites

An electron paramagnetic resonance study of Fe³⁺-doped cesium chloride single crystals was carried out at room temperature. Three sites are observed. The spin Hamiltonian parameters were determined from the angular variation of the observed resonance lines. The hyperfine structure is observed due to the presence of Fe⁵⁷ centers. At site I, Fe³⁺ enters the lattice substitutionally, replacing Cs⁺ in the cubic symmetry of the crystal, whereas at sites II and III, Fe³⁺ enters the lattice interstitially. The local site symmetry of Fe³⁺ in the host lattice is considered to be orthorhombic. An optical absorption study of the crystal was also performed at room temperature. The observed bands were assigned and the Racah inter-electronic repulsion parameters (B and C) and the cubic crystal field splitting parameter (Dq) were determined. On the basis of EPR and optical data, the nature of the metal–ligand bonding in the crystal was determined. The crystal field parameters were evaluated using the superposition model and then used in the microscopic spin Hamiltonian and perturbation equations to determine the zero-field splitting parameters (ZFSPs) theoretically for all sites observed. The theoretical ZFSPs are in good agreement with the experimental values.     

Spin relaxation for biradical spin probes in anisotropic environments

The large zero-field splitting of certain biradicals makes them important candidates for spin probes of anisotropic systems such as liquid crystals and membranes. The electron resonance spectrum of a biradical dissolved in a liquid crystal may be influenced by the zero-field splitting in two quite distinct ways. Firstly the line positions are affected because the spin probe is partially oriented by the liquid crystal solvent. In addition the zero-field splitting coupled with the molecular reorientation constitutes a powerful spin relaxation process and so may determine the widths of the spectral lines. Here we develop a theory of such line broadening, within the limit of fast motion, and show how it results in an angular dependence of the linewidths. The application of the theory is illustrated by studying the line broadening for a nitroxide biradical dissolved in a nematic mesophase. An analysis of the angular dependence of the linewidths suggests that the diffusion model provides a better account of molecular reorientation in a liquid crystal than the strong-collision approach. Finally we draw attention to the potential value of the theory for understanding the linewidth variations in the deuteron magnetic resonance spectra of liquid crystals.     

蓝宝石晶体的光谱精细结构、零场分裂参量及晶体结构

运用不可约张量算法和群理论构造了C3v对称晶场中3d5组念离子的252阶可完全对角化的微扰哈密顿矩阵.用此矩阵计算了Al2O3:Fe3 晶体的光谱精细结构、零场分裂参量(D,a-F)、品体结构,其理论计算值与实验值相符合,并研究了自旋四重态、自旋二重态分别对基态能级的影响,证明了自旋四重态对基态能级的贡献是主要的,自旋二重态对基态能级的贡献虽很小,但却是不可忽略的.进一步研究了SO梢合作用、SS耦合作用对Al2O3:Fe3-品体的光谱精细结构和零场分裂参量的影响,结果发现SO耦合作用是最主要的,SS耦合作用也是不可忽略的.     

Investigating the impurity structure for Fe3+ ions doped into rutile titanium dioxide single crystal

The local environment around Fe³⁺ centers in rutile TiO₂ crystals is studied by employing fourth-order perturbation theory formula based on the dominant spin–orbit coupling mechanism. The zero-field splitting parameters (ZFSPs) D and E and crystal field parameters are modeled for the Fe³⁺ ions not only at the substitution Ti⁴⁺ site, but also at the interstitial site with local symmetry D_2h. In order to acquire the best agreement between the calculated ZFSPs and those measured by electron magnetic resonance, the model parameters are adjusted on the basis of several approaches. This enables us to determine the feasible values of the structural distortions resulting from dopant Fe³⁺ ions. Consequently, it is confirmed that Fe³⁺ ions substitute for Ti⁴⁺ sites in rutile TiO₂ crystals.     

FeSiF66H2O晶体的基态能级和零场分裂参量

由单晶的中子衍射方法得到FeS_iF₆6H₂O的晶体结构,这种晶体结构可以用S_iF^6-和Fe(H₂O)⁺⁺两个离子来描述,而局域三角对称的Fe(H₂O)⁺⁺离子反映了这种晶体的主要光谱性质利用不可约张量的理论,构成了晶体场和自旋轨道相互作用哈密顿完全对角化矩阵因此,由完全对角化的晶体场和自旋轨道相互作用哈密顿矩阵和电子顺磁共振的理论公式来求出晶体FeS_iF₆6H₂O中Fe²⁺离子的电子顺磁共振零场分裂参量D和Fa并研究了低自旋³L态对电子顺磁共振(EPR)零场分裂参量的贡献结果显示低自旋³L态对电子顺磁共振的零场分裂参量的贡献是较强的理论计算的结果与实验值是相符的.     

Single-crystal (57)Fe Q-band ENDOR study of the 4 iron-4 sulfur cluster in its reduced [4Fe-4S](1+) state.

(57)Fe Q-band ENDOR has been used to study the [4Fe-4S](1+) state created by gamma irradiation of single crystals of the synthetic model compound [N(C(2)H(5))(4)](2)[Fe(4)S(4)(SCH(2)C(6)H(5))(4)] enriched in (57)Fe. This compound is an excellent biomimetic model of the active sites of many 4 iron-4 sulfur proteins, enabling detailed and systematic studies of its oxidized [4Fe-4S](3+) and reduced [4Fe-4S](1+) paramagnetic states. Taking advantage of the fact that Q-band ENDOR, in contrast with X-Band ENDOR, allows for a very good separation of the (57)Fe transitions from those of the protons, the complete hyperfine tensors of the four iron atoms for the [4Fe-4S](1+) species has been measured with precision. For each iron atom, the electron orbital and electron spin isotropic contributions have been determined separately. Moreover, it is remarkable that two (57)Fe hyperfine tensors attributed to the ferrous pair of iron atoms are very different. In effect, one tensor presents a much larger anisotropic part and a much smaller isotropic part than those of the other. This difference has been interpreted in terms of a differential electron orbital hyperfine interaction among the two ferrous ions.     

Zero-field splitting of <Superscript>4</Superscript><Emphasis Type="Italic">T</Emphasis><Subscript>2</Subscript> term for 3d<Superscript>3</Superscript> ions in tetragonal symmetry

By taking into account slight interactions, i.e. spin-spin, spin-other-orbit and orbit-orbit interactions, in addition to spin-orbit interaction, the zero-field splitting of ⁴ T ₂ state for 3d³ ions at tetragonal symmetry has been studied. The convergence of the approximation perturbation formula of ⁴ T ₂ state for 3d³ ions at tetragonal symmetry has been investigated, and the contributions to zero-field splitting arising from magnetic interaction and tetragonal crystal field are discussed. It is found that there exists combined mechanism between magnetic interactions and tetragonal crystal field.      

Electronic structure of ytterbium-implanted GaN at ambient and high pressure: experimental and crystal field studies

The results of high-pressure low-temperature optical measurements in a diamond-anvil cell of bulk gallium nitride crystals implanted with ytterbium are reported in combination with crystal field calculations of the Yb(3+) energy levels. Crystal field analysis of splitting of the (2)F(7/2) and (2)F(5/2) states has been performed, with the aim of assigning all features of the experimental luminescence spectra. A thorough analysis of the pressure behavior of the Yb(3+) luminescence lines in GaN allowed the determination of the ambient-pressure positions and pressure dependence of the Yb(3+) energy levels in the trigonal crystal field as well as the pressure-induced changes of the spin-orbit coupling coefficient.     

ZnSiF66H2O∶Fe2+晶体光谱结构的杨特勒效应和电子顺磁共振g因子

研究了过渡金属络合物ZnSiF66H2O∶Fe2+晶体光谱结构的杨特勒效应和电子顺磁共振g因子。由单晶的中子衍射方法得到ZnSiF66H2O∶Fe2+的晶体结构,这种结构可以用SiF2-6和Zn(H2O)++∶Fe2+两个离子来描述。而局域三角对称的Zn(H2O)++∶Fe2+离子反映了这种晶体的主要光谱性质。利用不可约张量的理论构成了晶体场和自旋轨道相互作用哈密顿矩阵和电子顺磁共振理论公式,求出了晶体ZnSiF66H2O∶Fe2+中Fe2+离子的电子顺磁共振零场分裂参量(D,F-a)及g因子,并研究了低自旋3L态对电子顺磁共振零场分裂参量的贡献是不能忽略的,而对g因子的贡献是非常小的,并理论计算了它的晶体结构,证实了杨特勒效应的存在,理论计算的结果与实验值是相符的。     

铜铁镁三掺铌酸锂晶体的第一性原理研究

利用基于密度泛函理论的第一性原理,研究了Cu:Fe:Mg:LiNbO3晶体及对比组的电子结构和光学特性.研究显示,单掺铜或铁铌酸锂晶体的杂质能级分别由Cu 3d轨道或Fe 3d轨道贡献,禁带宽度分别为3.45和3.42 eV;铜、铁共掺铌酸锂晶体杂质能级由Cu和Fe的3d轨道共同贡献,禁带宽度为3.24 eV,吸收峰分别在3.01,2.53和1.36 eV处;Cu:Fe:Mg:LiNbO3晶体中Mg^2+浓度低于阈值或高于阈值(阈值约为6.0 mol%)的禁带宽度分别为2.89 eV或3.30 eV,吸收峰分别位于2.45 eV,1.89 eV或2.89 eV,2.59 eV,2.24 eV.Mg^2+浓度高于阈值,会使吸收边较低于阈值情况红移;并使得部分Fe^3+占Nb位,引起晶体场改变,从而改变吸收峰位置和强度.双光存储应用中可选取2.9 eV作为擦除光,2.5 eV作为读取和写入光,选取Mg^2+浓度达到阈值的三掺晶体在增加动态范围和灵敏度等参量以及优化再现图像的质量等方面更具优势.     

ZnS∶Mn2+与ZnS∶Fe3+体系的基态零场分裂理论研究

在ZnS晶体中掺入Mn2 + 或Fe3 + 离子的EPR谱已得到了广泛的研究 .然而 ,理论结果显示其EPR零场分裂的计算值远小于实验观察值 ,这一理论与实验的矛盾至今仍未得到满意的解决 .假定在四面体ZnS中 ,S原子在成键时采取了sp3 杂化轨道的形式 ,从而使S离子显示出正的有效电荷 .从这一观点出发 ,通过对角化三角场中的微扰能量矩阵 ,使得ZnS∶Mn2 + 和ZnS∶Fe3 + 体系的EPR零场分裂参量α ,D和 (a -F)的实验值都能得到满意的解释. The EPR spectra of Mn 2+ and Fe 3+ ions in ZnS∶Mn 2+ and ZnS∶Fe 3+ systems have been extensively studied. However, the theoretical results show that the calculation values of the zero-field splitting are always much less than those of the experimental findings. Up to now, this difficulty has not yet been satisfactorily removed. In present paper, we assume that the sulfur ion has a sp 3 hybrid configuration in tetrahedral ZnS, so that the sulfur ion displays a positive...     

Mössbauer effect and electron spin resonance study of CdxMg1−xFe2O4 system

This work deals with the application of Mossbauer Effect (ME) in studying the crystal electric field and the cation distribution among tetrahedral (A) and the octahedral (B) sites of the spinal structure in the ferrite system Cd_x Mg_1–x Fe₂O₄ (x=0, 0.2,...1). The electron spin resonance technique (ESR) was also applied for studying this ferrite system. It was possible to characterize the ESR spectra of ferrite through the combination with the ME spectra.The ESR spectra of magnesium ferrite showed two resonance positions of Fe³⁺ ions and indicated that a strong exchange interaction is dominant in the pure Mg-ferrite. For high Cd concentration ferrites only single resonance line was observed. These results could be interpretted on the basis of the ME results where it indicated that Cd²⁺ ions prefer tetrahedral positions, forcing the Fe³⁺ ions from these positions to join those in the octahedral sites. The complete site occupation with different types of cations was successfully achieved from the ME spectra. The values of the quadrupole splitting indicated that for each ferrite in the system there exists an electric field gradient surrounding the Fe³⁺ ions in each of the octahedral and tetrahedral sites. The increase in the Mg-concentration increases the symmetry of the electric field at these sites.     

KCdF3:Cr3+晶体EPR零场分裂参量与电荷补偿效应的研究

按照叠加模型与EPR零场分裂参量的三阶微扰理论,建立了KCdF₃:Cr³⁺晶体EPR零场分裂参量与四角对称Cr³⁺-Cd²⁺缺陷中心局域结构之间的定量关系.证实Cd²⁺空位与晶格畸变的存在,我们获得:围绕Cr³⁺离子的六个F^-配体分别向中心Cr³⁺移动Δ₁=0.00294nm,Δ₂=0.0010nm,Δ₃=0.0028nm (参见图2).EPR零场分裂参量与实验一致表明:Cd²⁺空位与晶格畸变的假设是合理的.尽管四角晶场主要来自Cd²⁺空位,但晶格畸变的贡献不可忽略.     

EPR, Optical Absorption and Superposition Model Studies of Fe3+-Doped Diammonium Hexaaqua Magnesium Sulfate: A Case of Hyperfine Structure

An electron paramagnetic resonance (EPR) study of Fe³⁺-doped diammonium hexaaqua magnesium sulphate single crystal is carried out at liquid nitrogen temperature. EPR spectrum shows two sites. The spin-Hamiltonian parameters are evaluated from angular variation of observed hyperfine lines. Fe³⁺ ion enters the host lattice substitutionally at site I, replacing Mg²⁺, whereas it enters interstitially at site II. The local site symmetry of Fe³⁺ ion within the host lattice is orthorhombic. An optical absorption study is performed at room temperature. Using the optical absorption spectrum the bands are assigned and the Racah parameters (B and C) and cubic crystal field splitting parameter Dq are determined. The nature of metal–ligand bonding in the crystal is determined using EPR and optical data. Crystal field parameters and zero-field splitting parameters (ZFSPs) are evaluated theoretically for both the sites using superposition model and microscopic spin Hamiltonian together with perturbation equations, respectively. The theoretically evaluated ZFSPs are in good agreement with the experimental values.     

Electron paramagnetic resonance investigation of endohedral fullerenes N@C(60) and N@C(70) in a liquid crystal

Endohedral fullerenes N@C(60) and N@C(70) were dissolved in the liquid crystal 4-methoxybenzylidene-4'-n-butylaniline (MBBA) and investigated by electron paramagnetic resonance. In both cases well resolved EPR spectra give proof for molecular orientation in the nematic mesophase. Spectral features are dominated by a nonvanishing zero-field interaction, indicating a deviation from spherical spin density distribution at the encased nitrogen atom. In N@C(70), a maximum order parameter O(33) = 0.18(3), correlated with the long axis of the cage, and a zero-field-splitting parameter D = -2.6(4) MHz were determined. A persistent zero-field splitting is also observed in C(60) via the quartet spin of the encapsulated nitrogen, although no assignment of the director with respect to the molecular frame is possible. The observed line splitting is indicative of pseudo orientation of the rapidly rotating cage in this case.     

RbMgF3 ：Ni2+ 体系晶格局域结构的EPR理论研究

在考虑掺杂晶体局域畸变的影响后, 建立了联系RbMgF₃: Ni²⁺体系的局域畸变结构与EPR谱间的关系, 并计算了RbMgF₃: Ni²⁺晶体在C_3v和D_3d对称下的零场分裂参量和g 因数. EPR谱的理论计算值与实验值符合甚好.      

Electric field properties at cationic sites in normal, incommensurate and commensurate K2ZnCl4 crystals

The local electric properties at K and Zn sites in the normal, incommensurate and commensurate phases of K₂ZnCl₄, as derived from a numerical computation of the lattice contributions to the electric potential V(r), electric field intensityE(r) and electric field gradient tensorV _αβ(r) are reported. The numerical data obtained at each cationic position were correlated with the experimental³⁹K NMR, Cu²⁺ and Mn²⁺ EPR and⁵⁷Fe Mössbauer results in pure and doped K₂ZnCl₄. A proportionality between crystal field and zero-field splitting was taken into account for Mn²⁺, whereas for K⁺, Cu²⁺ and Fe³⁺ ions the electric field gradient is directly related to the crystal field parameter. By this comparison, on computations done in the ionic fractional charge and relaxed lattice approximations, the insertion of probe-species of iron, copper and manganese ions on off-center Zn sites is proposed. The³⁹K electric field gradient tensor calculations in the incommensurate phase fit well with the NMR data reported recently.     

(φ4As) CuCl3晶体中Cu2+-Cu2+离子对的EPR研究

本文在晶场理论的基础上,考虑了Cu²⁺-Cu²⁺离子间的交换作用后,得到了(φ₄As) CuCl₃晶体中Cu^2--Cu^2-离子对的跃迁能级,g-因子和零场分裂,计算结果与实验符合较好。