CaZrO3∶Mn^4＋晶体g因子及光谱的研究

推导了晶体中立方(Oh对称)的3d3八面体基团的g因子的高阶微扰公式;其中,既包括了传统的晶场机制(涉及与d—d跃迁光谱有关的晶场激发态与基态的相互作用)的贡献,也包括了以前在晶体场理论中被忽略的荷移机制(涉及与电荷转移光谱有关的荷移激发态与基态的相互作用)的贡献。采用这个公式和由CaZrO3∶Mn4 晶体光谱所得的参量,文章计算了该晶体的g因子(也包括了d—d跃迁光谱),计算结果与实验值能很好地吻合一致。计算中发现,荷移机制对g因子移动Δg(≈g-2.0023)的贡献在符号上与晶场机制的贡献相反,但大小已达到晶场机制贡献的62%。这表明,对晶体中高价态的3d3离子(如Mn4 和Fe5 )八面体基团,合理地解释其g因子(或其他电子顺磁共振谱参量)应同时考虑晶场机制和荷移机制的贡献。     

Ba2MgGe2O7:Cr4+晶体中荷移激发态对g因子贡献的研究

文章建立了立方四面体3d2络合物g因子的完全高阶微扰公式.在这个公式中,除了与d-d跃迁光谱(晶场激发态)有关的晶场(CF)机制的贡献(包括近年发展的双旋-轨耦合参量模型)外,与电荷转移光谱(荷移激发态)有关的荷移(CT)机制的贡献也被考虑.将这个公式应用于Ba2MgGe2O7:Cr4 晶体平均g因子的计算,发现理论计算值与实验值很好的一致,同时,荷移机制对g移动△g(=g-2.002 3)的贡献△gCT在符号上与晶场机制的贡献△gCF相反,而在大小上约为晶场机制贡献的38%.因此,在对高价态过渡金属离子络合物的g因子计算时应考虑CF机制和CT机制的贡献.     

Ba_2MgGe_2O_7∶Cr~(4+)晶体中荷移激发态对g因子贡献的研究

文章建立了立方四面体3d2络合物g因子的完全高阶微扰公式。在这个公式中,除了与d—d跃迁光谱(晶场激发态)有关的晶场(CF)机制的贡献(包括近年发展的双旋-轨耦合参量模型)外,与电荷转移光谱(荷移激发态)有关的荷移(CT)机制的贡献也被考虑。将这个公式应用于Ba2MgGe2O7∶Cr4 晶体平均g因子的计算,发现理论计算值与实验值很好的一致,同时,荷移机制对g移动Δg(=g-2.002 3)的贡献ΔgCT在符号上与晶场机制的贡献ΔgCF相反,而在大小上约为晶场机制贡献的38%。因此,在对高价态过渡金属离子络合物的g因子计算时应考虑CF机制和CT机制的贡献。     

ZnS:Co2+晶体顺磁g因子的理论研究

提出了一个计算二元半导体中过渡金属(TM)离子顺磁g因子的共价模型,并用以计算了ZnS:Co²⁺晶体的g因子,计算值与实验值吻合很好,从而解决了用经典方法得到的g因子值与实验值相比偏小的问题.同时,通过对ZnS:Co²⁺晶体晶场光谱和顺磁g因子的分析,本文建议,在ZnS:Co²⁺晶体中,Co²⁺离子的t_2g电子和e_g电子部分处于反键轨道部分处于成健轨道.     

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.     

ZnS:Co2+晶体的顺磁g因子研究

采用赵敏光提出的双zeta d-轨道模型,通过拟合平均共价性因子N和电偶极矩μ,统一地解释了ZnS:Co²+的d-d跃迁谱和顺磁g因子,g因子的计算结果分别为2.2482（微扰法）和2.235（完全对角化方法）,与实验值2.248符合得很好.文章对计算中遇到的轨道模型、微扰方法、参量拟合、双旋轨耦合及Jahn-Teller效应等有争议的问题作了阐释.     

KAl(MoO4)2晶体中掺杂Cr3+的能谱和g因子的理论计算*

采用强场方案和三角基，通过对角化三角畸变的立方晶场下的d3 完全能量矩阵，计算出了KAl(MoO4)2:Cr3+ 的能谱和波函数。使用对角化完全能量矩阵所获得的波函数，进一步计算了KAl(MoO4)2:Cr3+ 的基态g 因子。计算结果与光谱，EPR谱实验数据很好地符合。研究表明,利用对角化完全能量矩阵获得的波函数对 g 因子所作的计算为整个理论计算及波函数的归属提供了重要判据,充分体现了将能谱和g 因子作统一计算的重要性和必要性.     

CaF2:Co2+光谱和顺磁g因子的统一解释

基于半自洽场d轨道理论和完全对角化方法,从杂质局部结构统一解释了CaF₂:Co²⁺的光谱和顺磁 g 因子. 杂质局部结构存在塌缩效应,但仍保持八配位立方对称. 在此基础上,用微扰法和完全对角化方法讨论了g因子对晶场参量D_q的依赖关系. Macfarlane的 g 因子三阶微扰公式是好的近似公式,但随着D_q的减小,其有效性变差. 最后,文章讨论了基于完全对角化和自旋哈密顿理论的 g 因子公式的适用性,及其在轨道简并情况下的困难.     

RbNiCl_3晶体的局域结构、吸收光谱和顺磁g因子的统一解释

利用完全对角化方法和强场耦合方案,采用半自洽场(semi-SCF)自由Ni2 的d轨道模型,点电荷—偶极子模型和Ni2 -6X-(X=F,Cl,Br,I)络合物的μ-κ-α模型研究,建立了含有过渡族金属离子的晶体的局域结构与吸收光谱和顺磁g因子之间的定量关系,对RbNiCl3晶体的局域结构,吸收光谱和顺磁g因子作出了统一解释,所得理论计算结果与实验值符合得很好.这对进一步研究掺杂顺磁离子晶体的结构,光学,磁学,热学,电子顺磁共振参量,高压,精细结构等性质和了解晶体的结构信息提供了一种可行的方法.     

MgF2:Mn2+光谱、超精细常数和局部结构的关联

基于电子顺磁共振(EPR)超精细常数As确定键长的新方法和半自洽场d轨道理论,对MgF2:Mn2+光谱和EPR超精细常数作出了统一解释.得到室温下MgF2:Mn2+晶体中杂质中心Mn-F的键长为0.2124±0.0010nm.     

LaAlO3: Cr3+低温常压下的能谱和顺磁 g 因子的统一解释

利用配位场理论,在强场方案下,建立了包括立方晶场、库仑相互作用、自旋-轨道耦合、低对称场的d³完全能量矩阵,对LaAlO₃：Cr³⁺在低温常压下的能谱进行了拟合,确定了相应的参量,得到了与实验值比较相符的能谱,并利用所得的波函数计算了LaAlO₃：Cr³⁺基态的 g 因子,与实验结果相吻合. 根据所得参量分析了Cr³⁺与配位体之间相互作用的特性.     

Energy Spectra,g Factors and Their Pressure—Induced and ／or Thermal Shifts of SrTiO3：Cr^3＋ and SrTiO3：Mn^4＋ I：energy Spectra and g Factors at Normal Pressure

With the strong-field scheme and cubic bases,the complete d^3 energy matrix in a tetragonally distorted cubic-field has been constructed.By diagonalizing this matrix,the energy spectra of SrTiO3:Cr^3 and SrTiO3:Mn^4 at normal pressure and various temperatures have been calculated.Correspondingly,the FORTRAN program calculating the g factor of the ground state has been worked out.By using the program and the wavefunction obtained from diagonalizing the complete energy matrix,the g factors of the ground state of SrTiO3:Cr^3 and SrTiO3:Mn^4 at normal pressure and room temperature have been evaluated.The calculated results are in good agreement with the optical-spectral and EPR experimental data.The comparison and analysis of the results of two crystals have been made.It is demonstrated that the covalency of the bonding between Mn^4 and ligands(O^2-) in SrTiO3:Mn^4 is stronger than the one of the bonding between Cr^3 and ligands(O^2-)in SrTiO3:Cr^3 .It is shown that the obtained wavefunctions and values of parameters are reasonable.     

Energy Spectra,g Factors and Their Pressure-Induced and/or Thermal Shifts of SrTiO3:Cr3+ and SrTiO3:Mn4+ III: R-Line Thermal Shifts of SrTiO3:Mn4+

By taking into account all the irreducible representations and their components in the electron-phonon interaction (EPI) as well as all the levels and the admixtures of basic wavefunctions within d³ electronic configuration, the values of the parameters in the expressions of thermal shift (TS) from EPI for the ground level, R level and R line of SrTiO₃:Mn⁴⁺ have been evaluated; the R-line TS and various contributions to it have been calculated in the low-temperature region. It is found that all the three terms of R-line TS from EPI relevant to the lattice vibration are red shifts. The Raman term is the largest, the neighbor-level term is the second, and the optical-branch term is very small over the range of T≤80 K. The contribution to R-line TS from thermal expansion has been approximately neglected in this work. The very strong EPI relevant to its lattice vibration for SrTiO₃:Mn⁴⁺ causes its R-line TS to be an unusually large red-shift. Only by taking into account the strong softening of the low-frequency acoustic modes of the lattice vibration at low temperatures, can we successfully explain the variation of R-line TS of SrTiO₃$:Mn⁴⁺ with temperature.     

Energy Spectra and g Factors of α-A1203:Cr3+ and α-A1203:Mn4+

By diagonalizing the complete d³ energy matrix in a trigonally distorted cubicfield and using the wavefunctions from it, unified calculations of the whole energy spectrum as well as the g factors of the ground state and t₂^{3 2} E excited states for α-A1₂0₃:Cr³⁺ and α-A1₂0₃:Mn⁴⁺ have been carried out respectively. A11 the calculated results are in very good agreement with the experimental data. The comparison between the results of the two crystals has been made, which demonstrates that the covalency of α-A1₂0₃:Mn⁴⁺ is stronger than the one of α-A1₂0₃:Cr³⁺. For the zero-field splittings of the ground state and t₂^{3 2} E , their physical origins are revealed; the comparison and analysis of their values of the two crystals have been made.     

Tm3+掺杂CdWO4单晶的发光特性

用坩埚下降法生长获得了尺寸为φ25 mm×90 mm、Tm₂O₃初始掺杂摩尔分数为0.5%的CdWO₄单晶。晶体的颜色由上部血红色逐渐加深至下部的黑褐色。对不同部位的晶体薄片进行800 ℃的氧化处理,测定了处理前后不同部位的吸收光谱和FTIR红外光谱。经氧气退火处理后,由于氧空位缺陷减少,晶体的颜色明显变淡。在吸收光谱中观测到421,684,805 nm的吸收带。其中421 nm的吸收峰随退火温度的升高而逐步减弱,经800 ℃处理后基本消失。在808 nm激光二极管激发下,观察到中心波长为1.5 μm和1.8 μm的荧光发射,分别对应于Tm³⁺的³H₄→³F₄,³F₄→³H₆的能级跃迁。     

Theoretical Studies of Energy Spectra and g Factors of Cr3+-Doped YAl3(BO3)4

With the strong-field scheme and trigonal bases, by diagonalizing the complete d³ energy matrix in a trigonally distorted cubic-field, the energy spectra and wavefunctions of YAl₃(BO₃)₄:Cr³⁺ have been calculated. The rates of change of levels with respect to various parameters and the contributions to levels from various parameters are calculated, and the physical origins of various levels or splittings have been clearly and quantitatively shown. By using the wavefunctions obtained from diagonalizing the complete energy matrix, the g factors of the ground state of YAl₃(BO₃)₄:Cr³⁺ have been evaluated. The calculated results are in good agreement with the optical-spectral and EPR experimental data. It is demonstrated that the bonding between Cr³⁺ and ligands (O^2-) is ionic.     

镱掺杂钼酸铅的光谱和EPR谱的理论研究

该文表达了一个研究Yb³⁺掺杂PbMoO₄晶体的光谱和电子顺磁共振谱(EPR)的理论方法. 采用晶体场理论,推导了有关光谱和电子顺磁共振谱的公式. 基于这些理论公式,构建了4f¹³电子组态在D_2d晶体对称下包括Zeeman磁相互作用的14阶能量矩阵. 通过对角化这一能量矩阵,研究了Yb³⁺掺杂PbMoO₄晶体的光谱和电子顺磁共振谱. 所得的理论结果与实验值很好符合. 而且,相关的晶体场参量也在研究中确定.