Zeeman effect on the 4E level of Mn2+ in ZnS

The fine structure lines of the ⁴E level of Mn²⁺ in ZnS have been studied under a high magnetic field. Experiments were performed with the magnetic field parallel to the [111]_W crystallographic axis. The computed positions and intensities for polarized and non-polarized light are in agreement with the experiments.     

Mn2+ and Tl+ luminescence in β-aluminas

The compounds AGa₁₁O₁₇ (A = K, Rb, Cs) and AAl₁₁O₁₇ (A = Na, K, Rb) have the β-alumina structure. The Mn²⁺-activated gallates show efficient luminescence under 254 nm excitation with an emission peaking at 498 nm and a quantum efficiency up to 70%. The Tl⁺-activated aluminates show efficient luminescence under 254 nm excitation with an emission peaking at 380–390 nm and a quantum efficiency up to 70%. In AAl₁₁O₁₇: Tl⁺ energy is transferred from Tl⁺ to Mn²⁺, resulting in an emission peaking at 512 nm with a quantum efficiency up to 55%.     

纳米晶体ZnS：Mn2+发光寿命异常减缩机理的探讨

纳米晶体ZnS:Mn²⁺中Mn²⁺粒子⁴T₁→⁶A₁的发光寿命比晶体减缩了5个量级,这颇令人费解,因为通常解除自旋禁戒的磁作用远无如此强的效应.假定基质态的自旋不为零,且考虑了Mn²⁺的d电子和基质之间的交换库仑作用.若基质存在比Mn²⁺的⁴T₁激发态能量略高的某种激发态,则这种交换库仑作用将导致这两种激发态之间的混合,从而可解除发光能级弛豫中的自旋禁戒.这种混合随基质颗粒尺寸的减小而加强.我们并对此机制进行粗略的数值估计,给出了和实验相容的结果.     

Luminescence quantum efficiency of Mn2+ states in ZnS as studied by photoacoustic spectroscopy

Photoacoustic spectroscopy is employed to determine the luminescence quantum efficiency of Mn²⁺ in ZnS. Three spectra, photoacoustic spectrum, luminescence excitation spectrum and absorption spectrum, are compared. It is observed that the photoacoustic spectrum and the excitation spectrum behave complementarily. Radiative quantum efficiencies of the five excited states for Mn²⁺ have been determined.     

EPR study on Mn2+-Cu2+ and Ni2+-Cu2+ mixed pairs

An EPR study at X- and Q-band frequencies has been made on mixed metal pairs Mn²⁺-Cu²⁺ and Ni²⁺-Cu²⁺ obtained by doping the dimer complex C₅H₅NO CuCl₂ · H₂O. Available experimental data have been confirmed and extended, particularly as regards the characteristic directions of the various magnetic tensors. The qualitative behaviour of the spectra and the somewhat singular values of the magnetic parameters can be well-described on the basis of a theoretical model in which a very strong “cosine” interaction between the total electronic spins is assumed. From the model some interesting new aspects emerge, concerning the relations between pairs and single-ion EPR parameters.     

The ionic distribution in Mn2+ and Zn2+ β″-alumina

The ionic distributions in Mn²⁺ and Zn²⁺ β″-alumina (idealized formula: $\text{X}{}_{\mathrm{<mtext>5</mtext><mtext>6</mtext>}}\text{Mg}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{Al}{}_{\mathrm{<mtext>31</mtext><mtext>3</mtext>}}\text{O}{}_{17}\text{;}\text{X}\text{=}\text{Mn}\text{and}\text{Zn}\text{)}$ at 296 K are reported from single-crystal X-ray diffraction studies. Mn²⁺ β″-alumina exhibits the shortest c-axis found so far in any divalent β″-alumina: 33.141(3) Å;Zn²⁺ β″-alumina, which involves the smallest divalent ion studied in the frame-work, has a considerably longer c-axis: 33.517(3) Å. Both compounds show clear evidence of short-range correlation effects in the X²⁺ ion arrangement by way of departures from the centrosymmetric space-group $\text{R}\text{3}\text{m}$ of the β″-skeleton. Both 6c end-sites and 9d mO-sites ($\text{R}\text{3}\text{m}$ notation) are occupied for both ion-types, a significantly larger occupation (60% compared to 28% of the total) lying at or near the 9d mid-oxygen sites in Mn²⁺ β″-alumina compared to Zn²⁺ β″-alumina. Disorder is also found in the column-oxygen O(5) in both cases; the O(5) displacement from the 3b site in Mn²⁺ β″-alumina (0.59 Å) is the largest found in any divalent β″-alumina. The formula-unit/cell-layer, deduced on the basis of the amounts of X²⁺ ions refined, and assuming charge compensation through Mg substitution alone, are: Mn_0.79Mg_0.57Al_10.43O₁₇ and Zn_0.87Mg_0.74Al_10.26O₁₇.     

Fluorescence of Mn2+ in CaCO3

The fluorescence of Mn²⁺ ion as impurity in CaCO₃ has been investigated. Emission bands from the ⁴D(E_g), ⁴D(T_2g) and ⁴G(T_1g) levels have been observed. The analysis of excitation and emission spectra has allowed to obtain the values of field strength (Dq) for the excited energy levels of Mn²⁺ in CaCO₃ lattice. The temperature dependence of excitation and emission spectra yield an activation energy for thermal quenching of luminescence very close to theoretical calculation. The behaviour of luminescence lifetime with temperature has also been obtained.     

ESR study of Fe3+ and Mn2+ ions on trigonal sites in ilmenite structure MgTiO3

Electron spin resonance has been observed for Fe³⁺ and Mn²⁺ ions occupying sites with trigonal symmetry in undoped and doped Verneuil-grown crystals of the ilmenite type compound MgTiO₃. At 300 K, the fine structure parameters in the spin Hamiltonian are (in 10^?4cm^?1) D = +844 (± 1), (a? F) = +118 (± 1), a = 69 (± 7) for Fe³⁺ and D = +164 (± 1), (a ? F) = +10.2 (± l), a = 7.0 (± 1) for Mn²⁺. These values are compared with literature data for Fe³⁺ and Mn²⁺ in other oxides, especially Al₂o₃, with particular reference to the recent “superposition” theory of the effect of a trigonal distortion. From the orientation of the axes of cubic pseudosymmetry of the spin Hamiltonian, and with the assumption that a has the same sign for both ions, it is proposed that Fe³⁺ and Mn²⁺ occupy the same octahedral site, namely the Mg²⁺ site. Anomalous line splittings observed for one sample were attributed to twinning on (0001) or {1120} planes.     

Electronic absorption spectrum of Mn2+ ions doped in diglycine barium chloride monohydrate

The absorption spectrum of Mn²⁺ doped in diglycine barium chloride monohydrate has been studied at room temperature. The observed bands are assigned as transitions from the ${}^6\text{A}{}_{\mathrm{1g}}\text{(S)}$ ground state to various excited quartet levels of a Mn²⁺ ion in a cubic crystalline field. A new method has been suggested to evaluate the Racah parameters (B and C) accurately. The observed band positions are fitted with four parameters B, C, Dq and α, and the values obtained for the parameters are B= 810 cm^-1, C = 2990 cm^-1, Dq = 750 cm^-1 and α = 76 cm^-1.     

Optically detected E.P.R. of Mn2+ in faulted cubic ZnS

We have performed optically detected E.P.R. of Mn²⁺ in faulted cubic ZnS. This experiment permits the identification of the two axial E.P.R. spectra observed in these crystals. This identification allows an estimate of the D parameter of Mn²⁺ in wurtzite.     

EPR observation of phase transitions in calcium cadmium acetate hexahydrate: Using Mn2+ and Cu2+ ions as probe

Results of temperature dependence of EPR spectra of Mn²⁺ and Cu²⁺ ions doped calcium cadmium acetate hexahydrate (CaCd(CH₃COO)₄·6H₂O) have been reported. The investigation has been carried out in the temperature range between room temperature (～ 300 K) and liquid nitrogen temperature. A I-order phase transition at 146 ± 0.5 K has been confirmed. In addition a new II-order phase transition at 128 ± 1 K has been detected for the first time. There is evidence of large amplitude hindered rotations of CH₃ groups which become frozen at ～ 128 K. The incorporation of Cu²⁺ and Mn²⁺ probes at Ca²⁺ and Cd²⁺ sites respectively provide evidence that the phase transitions are caused by the molecular rearrangements of the common coordinating acetate groups between Ca²⁺ and Cd²⁺ sites. In contradiction to the previous reports of a change of symmetry from tetragonal to orthorhombic below 140 K, the symmetry of the host is concluded to remain tetragonal in all the three observed phases between room temperature and liquid nitrogen temperature.     

Cr2+: ZnS和Fe2+: ZnS光谱特性的比较研究

基于密度泛函理论和投影平面波方法,采用第一性原理对比分析了Cr2+: ZnS和Fe2+: ZnS 的电子结构和光学性能。晶体中二价掺杂离子的态密度、能带结构和几何优化由广义梯度近似的PBE描述。Cr2+: ZnS和Fe2+: ZnS的近中红外光谱表明,特征吸收来自于局域激发的d和p-d杂化轨道之间的跃迁,Fe2+: ZnS的中心跃迁能量比Cr2+: ZnS的要低,红移0.34 eV;分别制备了Cr2+: ZnS和Fe2+: ZnS晶体,并测得了Cr2+: ZnS和Fe2+: ZnS的吸收光谱,证实了Fe2+: ZnS的特征吸收峰较Cr2+: ZnS红移0.34 eV。     

Eu2+,Mn2+在BaZnP2O7中的发光及Eu2+→Mn2+能量传递

采用高温固相法合成了BaZnP₂O₇:Eu²⁺,Mn²⁺荧光粉,并对其发光性质及Eu²⁺对Mn²⁺的能量传递机理进行了研究.Eu²⁺和Mn²⁺在380 nm和670nm的发射峰分别由Eu²⁺的5d—4f跃迁和Mn²⁺的⁴T₁(^{4关键词： 磷酸盐 2+}')" href="#">Eu²⁺ 2+')" href="#">Mn²⁺ 能量传递     

Cr~(2+):ZnS和Fe~(2+):ZnS光谱特性的比较研究

基于密度泛函理论和投影平面波方法,采用第一性原理对比分析了Cr2+:ZnS和Fe2+:ZnS的电子结构和光学性能。晶体中二价掺杂离子的态密度、能带结构和几何优化由广义梯度近似的PBE描述。Cr2+:ZnS和Fe2+:ZnS的近中红外光谱表明,特征吸收来自于局域激发的d和p-d杂化轨道之间的跃迁,Fe2+:ZnS的中心跃迁能量比Cr2+:ZnS的要低,红移0.34eV;分别制备了Cr2+:ZnS和Fe2+:ZnS晶体,并测得了Cr2+:ZnS和Fe2+:ZnS的吸收光谱,证实了Fe2+:ZnS的特征吸收峰较Cr2+:ZnS红移0.34eV。     

Eu2+,Mn2+在BaZnP2O7中的发光及Eu2+→Mn2+能量传递

采用高温固相法合成了BaZnP₂O₇:Eu²⁺,Mn²⁺荧光粉，并对其发光性质及Eu²⁺对Mn²⁺的能量传递机理进行了研究.Eu²⁺和Mn²⁺在380 nm和670nm的发射峰分别由Eu²⁺的5d—4f跃迁和Mn²⁺的⁴T₁(^{4相似文献}   

EPR and luminescence of Mn2+ in MgF2 single crystals

EPR spectra of Mn²⁺ in MgF₂ crystals grown by the Bridgman technique were measured at 300 and 20 K. Application of the superposition model to the zero field splitting (ZFS) patterns indicates complete absence of dynamic contributions to the ZFS. The luminescence spectra are also in accord with substitutional incorporation of Mn²⁺.     

单晶LiNbO3:Mn2+的ESR谱研究

用室温电子自旋共振（ESR）实验研究单晶LiNbO3中Mn2+的精细结构和超精细结构.对ESR谱的分析得出,零磁场的能级分裂数值：自旋角动量能级±12〉与±32〉之间的间隔为Δε1=-587×10-4cm-1,而±32〉与±52〉之间的能级间隔为Δε2=-2633×10-4cm-1；其各向异性朗德因子g∥=21810，g⊥=20937；精细结构常数D=-536×10-4cm-1；超精细结构常数A∥=8836×10-4cm-1，A⊥=8120×10-4cm-1，即精细结构相互作用要比超精细结构相互作用大得多.另外，特别值得提到的是实验中还发现两组明显的禁戒跃迁，-32〉12〉和-12〉52〉. 关键词： 单晶 精细结构 超精细结构 禁戒跃迁