Spin-lattice coupling coefficients of Mn2+ ions in stacking faults of ZnS

The spin-lattice coupling coefficients (SLCC) of Mn²⁺ ions in axial sites PN of cubic ZnS crystals containing stacking faults have been measured by an uniaxial stress method. These coefficients were correctly interpreted in an ionic model by taking into account the Blume-Orbach mechanism adapted to a C_3v symmetry and a relativistic mechanism whose importance has been previously demonstrated. Finally, a comparison between the experimental SLCC's for Mn₂₊ in the cubic sites and two axial sites PN and AS due to stacking faults shows that they are roughly identical as predicted theoretically.     

Calculation of the probability of the 4 T 2→4 A 2 transition in luminescence spectra of the Mn4+ ion in gadolinium-gallium garnet

The ⁴ T ₂→⁴ A ₂ transition of the Mn⁴⁺ ion has been observed in the luminescence spectrum of Mn⁴⁺:Cd₃Ga₅O₁₂ upon intense laser pumping. It is shown that an increase in the intensity of the ⁴ T ₂→⁴ A ₂ transition with respect to the ² E→ ⁴ A ₂ transition in these crystals with increasing pumping power relates to the increased role of induced transitions. The intensity of this process is greater in the region where the ² E→⁴ A ₂ and ⁴ T ₂→⁴ A ₂ transition bands overlap most, which leads to an increase of the zero-phonon line of the latter transition, peaking at a wavelength of 694 nm. The rates of radiative and nonradiative recombination involving the ⁴ T ₂, ² E, and ⁴ A ₂ terms of the Mn⁴⁺ ion in gallium-gadolinium garnet (GGG) are calculated using data from luminescence spectra measured at different temperatures. The Mn⁴⁺:GGG crystal is proposed for use as an active element of lasers with continuous frequency tuning. __________ Translated from Optika i Spektroskopiya, Vol. 94, No. 4, 2003, pp. 590–596. Original Russian Text Copyright ? 2003 by Bulyarskiĭ, Zhukov, Prikhod’ko.     

On the Zeeman effect of 2Π states in diatomic molecules

The theory of the Zeeman effect in ²Π states of diatomic molecules is reconsidered. Second order terms due to the interaction with ²Δ states, which were left out in a previous investigation, are now included. The total correlation between the spin-rotation coupling constant and the centrifugal distortion in the spin-orbit coupling renders the fitted molecular g factors somewhat ambiguous. This problem is handled by a transformation of the basis for the Hamiltonian matrix. The theoretical results are exemplified for the ²Π ground state of OH for which EPR data are available for both the ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ substates. A combination of ab initio predictions and fitted values of the g factors finally yields new information concerning the separate contributions from ²Σ⁺, ²Σ^?, and ²Δ states to the contamination of the ²Π ground state in OH.     

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.     

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.     

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.     

Trapping effects in the luminescence of Zn2GeO4:Mn2+

Free carriers are created in this material under sub-band-gap excitation and the effects of these on the luminescence are studied. The slow rise of emission, long afterglow and infrared stimulability are explained with a model utilizing an empirical set of configuration coordinate curves. The rise and afterglow curves are fitted to solutions to a rate equation which is based on the postulation of only one kind of trapping center.     

Ion source effect on the bond length of ^4HeH^＋

The bond length of ^4HeH^＋ resulting from collision-induced destruction is measured at 1.4420 MeV using the Coulomb Explosion Technique. The measured bond length of ^4HeH^＋ is 0.094±0.003nm. The bond length of ^4HeH^＋ obtained with our radio frequency （RF） ion source is larger than that obtained with a duoplasmatron ion source at Argonne National Laboratory （ANL）, but the bond lengths of H^＋2 and H^＋3obtained separately by ANL and by us with the two different ion sources are consistent with each other, which implies that there exists an ion source effect on the bond length of ^4HeH^＋. The main reason why the 4^4HeH^＋ bond lengths obtained by the two different ion sources are different is also discussed.     

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。     

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.     

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。     

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.     

Absolute quantum yields of Cr3+2E → 4A2 emission in solids

The absolute quantum yields of powders have been obtained. The correction factors involved in using this method are described. The room temperature yield of ruby, 0.63 (⁴T₂←⁴A₂ excitation), is in good agreement with the previously reported single crystal results. No change in ruby quantum yield accompanies temperature reduction to 80°K. The absolute quantum yields of dilute (1–2%) Cr³⁺ in NaMgAl (C₂O₄)₃?9H₂O powders are 0.27 at 80°K. A small but measurable concentration dependence is observed with this system. Evidence to support an intramolecular intersystem crossing efficiency of unity is presented.     

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.     

Ba2SiO4:Ce3+,Mn2+荧光粉的制备与光谱性质

用高温固相反应法合成了Ba₂SiO₄:xCe³⁺,yMn²⁺(x=0~0.2, y=0~0.15)荧光粉,研究了荧光粉的晶体结构和发光性质。在紫外光激发下,Ba₂SiO₄:xCe³⁺的发射光谱为位于384 nm附近的宽带。Ba₂SiO₄:Mn²⁺样品的发射光谱位于376 nm的宽带较强,红光发射极弱。在Ce³⁺和Mn²⁺共掺的Ba₂SiO₄:xCe³⁺,yMn²⁺样品中,位于606 nm附近的红光发射较强,来源于Mn²⁺的⁴T₁(⁴G)-⁶A₁(⁶S)跃迁。这说明Ce³⁺离子将部分能量传递给了Mn²⁺离子,有效地敏化了Mn²⁺离子的发光。当Ce³⁺的摩尔分数为0.2、Mn²⁺的摩尔分数为0.075时,Ba₂SiO₄:xCe³⁺,yMn²⁺荧光粉位于606 nm的Mn²⁺的发射峰最强。     

近红外到近红外Mn2+掺杂NaYF4:Yb3+/Tm3+纳米粒子的制备及其生物成像

在反应温度为200℃、反应时间为8 h的温和条件下,采用水热法合成了近红外到近红外的Mn²⁺掺杂NaYF₄:Yb³⁺/Tm³⁺上转换荧光纳米粒子,再以两亲性聚合物C₁₈PMH-mPEG作为亲水性配体修饰到上转换荧光纳米粒子表面,得到具有水溶性的上转换荧光纳米粒子。然后在980 nm近红外光源激发下,测量了上转换荧光纳米粒子的荧光发射光谱,在（800±10） nm附近,观察到了较强的单近红外光发射（³H₄→³H₆）。对样品进行细胞毒性实验,结果表明制得的水溶性Mn²⁺掺杂NaYF₄:Yb³⁺/Tm³⁺纳米粒子具有良好的生物相容性。并进一步在小鼠体内进行了近红外成像,表明其在生物成像领域将会具有一定的应用前景。     

Mn2+ paramagnetic resonance and structural phase transitions in Rb2CdCl4

Structural phase transition in Rb₂CdCl₄: Mn²⁺ single crystal has been found near 133 K by EPR, X-ray and optical methods. Octahedral tilt system in the low temperature phase corresponds to the symmetry change D¹⁷_4h → D¹⁸_2h or D¹⁷_4h → C⁶_2h.