稀土化合物RX的晶场参数分析

本文对NaCl型结构的稀土化合物RX(X=N,P,As,Sb,Bi)的晶场参数B₄⁰的实验值进行了分析。在此基础上我们提出一个新的利用简单点电荷模型计算RX晶场参数B₄⁰值的关系式:B₄⁰=k₃(B₄⁰)_p+c₃。用此关系式我们确定了一系列RX的晶场参数B₄⁰值,结果与实验值符合很好。对关系式的含义本文也作了充分讨论。 关键词：     

Optical properties of LiNbO3:Cr crystals co-doped with germanium oxide

Lithium niobate (LiNbO₃) crystals doped with chromium ions show a clear green colouring reflecting the absorption profile of the dominating [Cr]_Li defect centres. A significant change in its colouration takes place when it is co-doped with other valency impurities such as Mg²⁺, Sc³⁺ and W⁶⁺, above a certain threshold concentration. This concentration singularity has been attributed to the formation of [Cr]_Nb centres coexisting with the [Cr]_Li centres.In this work, we extended the investigation on the effect of co-dopant ions in Cr:LiNbO₃ to tetravalent cation such as GeO₂. A singularity in the relative intensity of the ⁴A₂→⁴T₁ and ⁴A₂→⁴T₂ absorption band was observed for a concentration of ～1.5 mol%, compared with 4.5 mol% for Mg²⁺. The photoluminescence emission spectra also reveal a new emission band, at a lower energy than the [Cr]_Li centre, corresponding to this threshold concentration. A charge compensation model is proposed to explain the role of cation impurities and results are compared with those of other valence impurities.     

89Yttrium nuclear magnetic resonance studies

With a Fourier-transform spectrometer, especially developed for nuclei with weak NMR signals, the lines of⁸⁹Y have been investigated in aqueous solutions of Y(NO₃)₃, YCl₃, and Y(ClO₄)₃. The concentration dependence of the chemical shifts of the⁸⁹Y resonance frequencies in these solutions were measured. Using this dependence, the Larmor frequency of the⁸⁹Y³⁺ ion solely surrounded by water was determined by extrapolation. The Larmor frequency of⁸⁹Y was referred to those of²H,³⁹K, and⁷³Ge with high accuracy. The magnetic moment of the⁸⁹Y³⁺ ion purely surrounded by H₂O molecules is μ(⁸⁹Y³⁺) = ?0.1368523(4) μ_N. The concentration dependence of Y(NO₃)₃ solutions in D₂O yields the solvent isotope effect δ(⁸⁹Y³⁺ in D₂O)?δ(⁸⁹Y³⁺ in H₂O)= ?(4.3±0.5)ppm. The⁸⁹Y relaxation times T₁ and T₂ of a 3 molal aqueous Y(NO₃)₃ solution were determined in the pH range ?0.5...+1.25. T₁ 190...90 s is nearly constant in this range, whereas the transverse relaxation rate T₂ ^?1 increases strongly with increasing pH; this effect seems to be due to the chemical exchange of the hydrated Y³⁺ ion between a monomer and a polymer site.     

MCsn cluster formation on organic surfaces: A novel way to depth-profile organics?

In this work, we investigated the bombardment of polymer surfaces (PC, PMMA) with very low energy (250 eV) Cs⁺ ions.In the positive mode, we observed many cations combining a molecular fragment of the polymer (M) with two Cs atoms, similar to the well-known MCs₂⁺ clusters commonly observed in inorganic depth profiling with Cs. For example, Cs₂COOH⁺ or Cs₂C₆H₅O⁺ were measured on PC and Cs₂CH₃O⁺ or Cs₂C₄H₅O₂⁺ were measured on PMMA. In fact, most of the polymer characteristic fragments measured in negative spectra also appear in the positive spectra, combined with two Cs atoms. It is remarkable that stable negative ions tend to combine not with one Cs, but with two Cs atoms to create the MCs₂⁺ cluster.This effect is, to some extent, similar to the well-known cationisation of polymers (with Ag or Au) although here few clusters with only one Cs atom are detected (MCs⁺ clusters), like in classical cationisation. The most abundant clusters are the MCs₂⁺ clusters, but heavier clusters (MCs₃⁺, MCs₄⁺ and above) are also measured with high yields in the spectrum.Surprisingly, some of those MCs₂⁺ clusters were still detected even after a very long sputtering fluence (above 10¹⁷ ions/cm²), proving that some molecular depth profiling is also possible in this “Cs₂-cationisation” mode. In other words, this work could open the way to an extension of the MCs_n⁺ cluster analysis, commonly used in inorganic depth profiling, to the in-depth molecular analysis of organic layers.     

Optical properties of Sm3+ and Dy3+ ions in Gd2MoB2O9 host lattice

Gd₂MoB₂O₉ doped with Sm³⁺ and Dy³⁺ were used for this study. The photoluminescence behaviors of Sm³⁺ and Dy³⁺ in this phosphor material were investigated by the excitation and emission spectra. The Sm³⁺-doped Gd₂MoB₂O₉ phosphor powders show a red luminescence, whereas the Dy³⁺-doped Gd₂MoB₂O₉ phosphor powders show a yellow luminescence. In addition, the optimum doping concentration and the time-resolved luminescence spectroscopy were also investigated.     

Diffractive production of two ρ<Superscript>0</Superscript><Subscript>L</Subscript> mesons in e<Superscript>+</Superscript>e<Superscript>-</Superscript> collisions

We present an estimate of the cross-section for the exclusive production of a ρ_L ⁰-meson pair in e⁺e^- scattering, which will be studied in the future high-energy International Linear Collider. For this aim, we complete calculations of the Born order approximation of the amplitudes γ^* _L,T(Q₁ ²)γ^* _L,T(Q₂ ²)→ρ_L ⁰ρ_L ⁰, for arbitrary polarization of virtual photons and longitudinally polarized mesons, in the kinematical region s≫-t,Q₁ ²,Q₂ ². These processes are completely calculable in the hard region Q₁ ²,Q₂ ²≫Λ² _QCD, and we perform most of the calculations in an analytical way. The resulting cross-section turns out to be large enough for this process to be measurable with foreseen luminosity and energy, for Q₁ ² and Q₂ ² in the range of a few GeV².     

Co-doping effect of SnO2 and ZnO in In2O3 ceramics: Change in solubility limit and electrical properties

In this study, SnO₂ and ZnO were co-doped in In₂O₃, and the phase development and electrical characteristics were examined. When Zn²⁺ was added to 20 at.% Sn⁴⁺ contained In₂O₃, in which a large amount of In₄Sn₃O₁₂ second phase exists, the amount of the second phase decreased as the content of Zn²⁺ increased, which promoted grain growth and increased carrier mobility. In the case of a simultaneous substitution of Sn⁴⁺ and Zn²⁺ into In₂O₃ with almost the same atomic ratio, a large grain size without second phase was observed, while small grain sizes with many second phases were developed when Sn⁴⁺ and Zn²⁺ were added with different atomic ratios. The electrical characteristics analyzed by Hall effect measurement showed that the electron mobility and conductivity showed a close relationship with the microstructure, while the carrier concentration was almost constant regardless of the Zn²⁺ content.     

124Te核1+态和高自旋态能谱特征的微观研究

利用微观sdIBM-2+2q.p.方案，成功地计算出¹²⁴Te核的低自旋态和部分高自旋态，特别是较成功地再现了1⁺₁,1⁺₂,3⁺₁，3⁺₂和5⁺₁态.基于该方案推出的能量关系指认：6⁺₁，8⁺_{关键词： 能谱特征 拆对与顺排 微观sdIBM-2+2q.p.方案 124Te核')" href="#">¹²⁴Te核}     

Feasibility Study on Quantitative Measurements of Singlet Oxygen Generation Using Singlet Oxygen Sensor Green

The purpose of this study is to investigate the feasibility for quantitative measurement of singlet oxygen (¹O₂) generation by using a newly developed ¹O₂-specific fluorescence probe Singlet Oxygen Sensor Green reagent (SOSG). ¹O₂ generation from photoirradiation of a model photosensitizer Rose Bengal (RB), in initially air-statured phosphate buffered saline (PBS) was indirectly monitored with SOSG. In the presence of ¹O₂, SOSG can react with ¹O₂ to produce SOSG endoperoxides (SOSG-EP) that emit strong green fluorescence with the maximum at 531 nm. The green fluorescence of SOSG-EP is mainly dependent on the initial concentrations of RB and SOSG, and the photoirradiation time for ¹O₂ generation. Furthermore, kinetic analysis of the RB-sensitized photooxidation of SOSG is performed that, for the first time, allows quantitative measurement of ¹O₂ generation directly from the determination of reaction rate. In addition, the obtained ¹O₂ quantum yield of porphyrin-based photosensitizer hematoporphyrin monomethyl ether (HMME) in PBS by using SOSG is in good agreement with the value that independently determined by using direct measurement of ¹O₂ luminescence. The results of this study clearly demonstrate that the quantitative measurement of ¹O₂ generation using SOSG can be achieved by determining the reaction rate with an appropriate measurement protocol.     

Energy transfer and fluorescence characteristics of erbium-doped ytterbium aluminum garnet

We have examined the fluorescence characteristics of the garnet-type crystal Yb₃Al₅O₁₂ : Er³⁺ (YbAlG : Er³⁺) and studied the energy transfer process between the two rare earth ions over a temperature range 78–297 K. Certain data were compared with those of YAlG : Er³⁺. In YbAlG : Er³⁺, Yb fluorescence is observed at ?1.03 μm (corresponding to the ²F_5/2 → ²F_7/2 transition); Er fluorescence occurs at ?8500 Å (⁴S_3/2 → ⁴I_13/2 transition) and ?1.6 μm (⁴I_13/2 → ⁴I_15/2 transition). In YAlG : Er³⁺, the same Er lines are observed with the addition of a band at ?1 μ (⁴I_11/2→⁴I_15/2 transition). In YbAlG : Er³⁺, the decay pattern of the Yb emission is purely exponential at all the temperatures examined; the fluorescence lifetime ranges from 36 μ s (at 78 K) to 74 μs(at 269 K). The lifetime of the Er⁴I_13/2 level in the same sample increases from 5.4 ms (at 78 K) to 6.85 ms (at 294 K). The lifetime of this Er level in YAlG : Er³⁺ is weakly temperature dependent over the same range with a value of ?12 ms. Excitation spectra were obtained for the Er 1.53 μm fluorescence in YbAlG : Er³⁺ in order to verify the presence of Yb → Er energy transfer in this sample. The presence of the Yb absorption band (?1 μm) in these spectra provides direct evidence of this energy transfer. The relative enhancement of this Yb band with respect to the Er bands in going from 78 K to 175 K is an indication of a more efficient transfer at the higher temperature. Excitation spectra obtained for the Yb 1.03 μm fluorescence in YbAlG : Er³⁺ revealed the presence of Er → Yb energy transfer as well in this sample. The existence of both Yb → Er and Er → Yb transfer is expected, due to the resonance between the ⁴I_11/2 → ⁴I_15/2 transition of Er and the ²F_5/2 → ²F_7/2 transition of Yb. The above results are explained in terms of a rate equation model in which transfer in both directions is treated in the following manner: Yb → Er transfer is considered to be much more probable than decay processes originating at the Yb ²F_5/2 level; Er → Yb transfer is treated as much more probable than decay processes originating at the Er ⁴I_11/2 level.     

Optical spectra of (CdF2)0.9(InF3)0.1 semiconductor solid solutions

The differences in the optical spectra of CdF₂:In semiconductors with bistable DX centers (concentrated (CdF₂)_0.9(InF₃)_0.1 solid solutions) and “standard” samples with a lower impurity concentration used to record holograms are discussed. In contrast to the standard samples, in which complete decay of two-electron DX states and transfer of electrons to shallow donor levels may occur at low temperatures, long-term irradiation of a (CdF₂)_0.9(InF₃)_0.1 solid solution by UV or visible light leads to decay of no more than 20% deep centers. The experimental data and estimates of the statistical distribution of electrons over energy levels in this crystal give the total electron concentration, neutral donor concentration, and concentration of deep two-electron centers to be ～5 × 10¹⁸ cm^?3, ～9 × 10¹⁷ cm^?3, and more than 1 × 10²⁰ cm^?3, respectively. These estimates show that the majority of impurity ions are located in clusters and can form only deep two-electron states in CdF₂ crystals with a high indium content. In this case, In³⁺ ions in a limited concentration (In³⁺ (～9 × 10¹⁷ cm^?3) are statistically distributed in the “unperturbed” CdF₂ lattice and, as in low-concentrated samples, form DX centers, which possess both shallow hydrogen-like and deep two-electron states.     

Absorption spectra of C6H6 and C6D6 near 340 nm

The absorption spectra of C₆H₆ and C₆D₆ in the liquid phase have been studied near 340 nm. The absorption spectrophotometric mounting was a sequential double-beam attachment with linear response to energy on scanning of the spectrum before the exit slit and an electronic device which gives directly either the absorbance or the integrated absorbance of a transition and, consequently, its oscillator strength.The oscillator strength measured for the band of C₆H₆ is 8×10^?8, which corresponds to a dipole moment of 2.4×10^?3 Debye; this value is of the same order as a theoretical value calculated by Tsubomura and Mulliken (3.8×10^?3 Debye) for a transition between states ³F and ³A of an oxygen-benzene pair. This agreement corroborates the hypothetical existence of such a transition.The first vibrational band is at 28553 cm^?1 for C₆H₆; this band is not observed in the vapor or solid phase. It corresponds probably to the transition 0-0, which is considered in the literature to be near 29500 cm^?1. The isotopic shift measured for this first band is 164 cm^?1. The vibrational frequencies are, respectively, 910 cm^?1 for C₆H₆ and 889 cm^?1 for C₆D₆.     

Synthesis,TGA and EPR studies of phase transitions in Cu2+ doped (NH4)4ThF8 and (NH4)3ThF7

The paper presents the EPR evidence for the occurrence of phase transitions in (NH₄)₄ThF₈ and (NH₄)₃ThF₇. In both cases the Cu²⁺ probe occupies a NH⁴⁺ site and predominantly experiences a dynamic coordination, either due to dynamic Jahn-Teller effect, or due to fluxional behaviour of surrounding (ThF₈)^4- units in (NH₄)₄ThF₈. It is proposed that the structural phase transition in this compound at 214 K is associated with the transition of the dynamic coordination of Cu^2- into a static one, probably due to freezing of motion of (ThF₈)^4- units below this temperature. In (NH₄)₃ThF₇ the dynamic features of the Cu²⁺ EPR spectrum are absent and characteristics of a local orthorhombic symmetry are seen down to 77 K. However, in the high temperature range a change from orthorhombic to axial symmetry is observed at 524 K, possibly due to a phase transition.     

The infrared spectrum of diazirine: . Rovibrational analysis of the ν3 fundamental

Diazirine is one of the seven possible isomers of diazomethane. The medium-resolution infrared spectrum of this cyclic compound, which seems to be very stable in the gas phase, was reported by Ettinger. The mid-infrared spectra of diazirine and of the substituted isotopic species D₂CN₂, H₂¹³CN₂, and H₂C¹⁵N₂ were recorded with a resolution of 0.08 cm^?1. The overall assignment of these spectra is reported here. The ν₃ fundamental of the main species at 1459.15 cm^?1 (CH₂ deformation) is an A-type parallel band but presents a complicated band structure since diazirine is an asymmetric rotor with κ = ?0.427. The rovibrational assignment and the analysis of this band, together with the determination of the molecular constants, is given.     

Crystal field efects on the electron spin resonance of rare-earths in YPd3: Comparison with inelastic neutrons scattering experiments

We report low temperature Electron Spin Resonance experiments on diluted Er, Dy and Yb in YPd₃. The host cubic crystal field leaves a Γ₆ ground state for Er³⁺, and a Γ₇ excited state could be observed at 18 ± 4K for this system. A lower lying Γ₇ was measured for Yb³⁺ in YPd₃, and a broad undefined resonance for Dy³⁺ in this host. A comparison of our data with those obtained by Inelastic Neutrons Scattering is given.     

Λc(2940)+: a possible molecular state?

A new baryonic state Λ_c(2940)⁺ has recently been discovered by the Babar collaboration in the D⁰p channel. Later Belle collaboration also observed this state in the Σ_c(2455)^0,++π^±→Λ_c ⁺π⁺π^- channel. The mass of Λ_c(2940)⁺ is just a few MeV below the sum of D^*0 and p masses suggesting a possibility that this state may be a D^*0p molecular state. In this paper we study whether such a molecular state can be consistent with data. We find that the molecular structure can explain data and that if Λ_c(2940)⁺ is a D^*0p molecular state it is likely a 1/2^- state. Several other decays modes are also suggested to further test the molecular structure of Λ_c ⁺(2940). PACS 13.30.Eg; 14.20.Lg; 12.39.Pn     

Thermochemistry of the reactions between CN+ and H2O in the gas phase

The [H₂, C, N, 0]⁺ potential energy surface (PES) has been explored by means of high-level ab initio calculations, carried out in the framework of the G2 theory. From this survey we concluded that the predominant products of the CN⁺ + H₂O reaction are the result of the dissociation of HNCOH⁺ species and to a much lesser extent of the CNHOH⁺ cation to yield CNH⁺ + OH. According to our results HCN⁺ should not be a product of this reaction because all pathways leading to its formation are unfavourable with regards to other competitive processes. Other reactive channels lead to the formation of the H₂ONC⁺ structure which dissociates into CN + H₂O⁺. The loss of NH(3σ) and O(³P) seems to take place following spin-forbidden reaction paths through an intersystem crossing between the singlet and the triplet PESs. The global minimum of the PES, H₂NCO⁺ is easily accessible and should lead to the loss of carbon monoxide which has not been experimentally observed in CN⁺ + H₂O reactions. We cannot offer a clear explanation for this disagreement between theory and experiment.     

Spectroscopic investigation of CaFeSn(PO4)3

Infrared and Raman spectra of CaFeSn(PO₄)₃ have been recorded and discussed with the aid of a site-symmetry analysis. The Mössbauer (⁵⁷₁₁₉Fe and ¹¹⁹Sn) spectra of this compound as well as the Sn-spectra of KSn₂(PO₄)₃ and TlSn₂(PO₄)₃ were also reported. The obtained spectroscopic information allows a deeper insight into the structural and electronic properties of this type of solids.     

A cross-relaxation mechanism of fluorescence quenching in complexes of lanthanide ions with organic ligands

For the first time, direct experimental evidence of a new mechanism for the quenching of fluorescence of organic ligands (L) in complex compounds with lanthanide ions (Ln³⁺) is obtained. By analogy with the mechanism of luminescence quenching upon pair interactions of Ln³⁺ ions in inorganic systems, this mechanism is called the cross-relaxation mechanism. The experiments are performed with complexes of Tb³⁺ with dianions of halogen-substituted fluoresceins (HSFs): 4,5-dibromo-and 4,5-diiodofluorescein, eosin B, eosin, erythrosin, and Rose Bengal in dimethyl sulfoxide. In accordance with this mechanism—exchange energy transfer, L^2?(*S ₁), Tb³⁺(⁷ F ₆)→L^2?(T ₁), Tb³⁺(⁷ F _{5, 4}), allowed by the spin selection rules—an increase in the quantum yield of formation of the triplet state (Φ_T) of a ligand L^2? and a decrease in the quantum yield of fluorescence (Φ_fl) are found to take place upon complexation. The efficiency of this process amounts to ～1 in accordance with the equality Φ_fl+Φ_T=1, valid for solutions of HSFs. The possibility of other processes leading to a similar effect, specifically, recharging of the system (as for complexes of HSFs with Eu³⁺ and ³⁺) is considered. An example of inductive resonance interactions in complexes of HSFs with Pr³⁺ is given. The manifestation of equilibrium between outer-sphere and inner-sphere complexes in the photophysics of complexes of metals with HSFs is discussed.

     

Experimental study of the energy dependence of the reaction rate coefficients of the reaction CH 3 + with N2O and NH3

The kinetics of the reaction of CH ₃ ⁺ ions with N₂O and NH₃ has been investigated in He and Ar buffers using Selected Ion Flow Drift Tube technique (SIFDT). Both studied reactions proceed with nearly collisional rate at near thermal energies. The rate coefficient of the reaction of CH ₃ ⁺ with N₂O is decreasing more than one order of magnitude (from 1.2×10^?9cm³s^?1 up to 8×10^?11cm³s^?1) with reactant ion/reactant neutral average centre-of-mass kinetic energy (E _r) increasing from near thermal up to 2 eV. The dominant product of this reaction is the isomer HCO⁺ (≥94%) and the minor product is CH₃O⁺. The reaction of CH ₃ ⁺ with NH₃ has two binary channels with the dominant product ion CH₂NH ₂ ⁺ (>70%) and the minor product ion NH ₄ ⁺ (≈10%) and three body association channel with product CH₃NH ₃ ⁺ (≈20% at 0.32 Torr). The rate coefficient of this reaction is decreasing nearly by one order of magnitude with increasingE _r from near thermal up to 0.8eV, forE _r>0.8 eV the rate coefficient increases with increasingE _r. The experimental results are interpreted in terms of a simple model assuming the reactions to proceed via the formation of long-lived collision complexes.