5d–4f luminescence of Ce3+, Gd3+ and Lu3+ in LiCaAlF6

The emission and excitation spectra as well as decay kinetics of luminescence due to 5d–4f transitions in Ce³⁺, Gd³⁺ and Lu³⁺ ions doped into LiCaAlF₆ crystals have been analyzed with high spectral and time resolution using synchrotron radiation for excitation. The rich fine structure originating from electronic origins of transitions and their phonon replica has been well resolved and identified. Experimental data are compared with the spectra simulated in the framework of the semiphenomenological models of the crystal field and the crystal lattice dynamics.     

Broadening of the lines due to the 4f n -4f n − 15d transitions of Ce3+, Pr3+, and Tb3+ ions in the absorption spectra of CdF2 crystals

The structure of the absorption spectra of Ce³⁺, Pr³⁺, and Tb³⁺ ions in the vicinity of 4f-5d transitions has been investigated. At low temperatures the absorption spectra exhibit a weakly pronounced fine structure, in contrast to narrow-line spectra in crystals of Ca, Sr, and Ba fluorides. The spectra of Ce³⁺, Pr³⁺, and Tb³⁺ ions in CdF₂ can be considered as the absorption spectra of these ions in alkali-earth fluorides, broadened by 60–75 cm^?1. The broadening is related to the autoionization of electron from the local 5d(e _g ) level to the energy-degenerate states of the conduction band of CdF₂ crystal.     

Calculated local density X-ray and photoemission spectra for superconducting La2−xMxCuO4: Localization of Cu-3d

Comparison of UPS (XPS) and XES spectra for the high T_c superconductor La_2−xM_xCuO₄ - calculated using highly precise local density results - with available experimental data reveals a large shift of about 2 eV to lower energies for the Cu-d related features. This shift is interpreted qualitatively in terms of a simple two-level model taking into account the hole-hole repulsion at the Cu sites in the photoemission final state. This simple model explains nicely the magnitude of the shift, the occurence of a Cu related satellite below the valence-bands, and the charge-transfer screening of the Cu-d photo-holes by O-p electrons. The O-states, especially the bonding states at the bottom of the valence band, are less affected and agree reasonably well with the experimental findings.     

Ultraviolet luminescence of Li6Gd(BO3)3: Ce crystals under selective excitation in the region of 4d → 4f transitions

The subnanosecond time-resolved ultraviolet luminescence of Li₆Gd(BO₃)₃: Ce crystals under selective excitation by ultrasoft X-rays in the region of the 4d??4f core transitions at temperatures of 7 and 293 K has been investigated for the first time. The performed investigation has revealed the following features: an intense fast component of the luminescence decay kinetics in the subnanosecond range due to the high local density of electronic excitations and the processes of Auger relaxation of the core hole; the modulation of the luminescence excitation spectrum by the ??giant resonance?? absorption band of the 4d-4f photoionization in the energy range 135?C160 eV; and a new broad luminescence band at an energy of 4.44 eV due to the direct radiative recombination between the genetically related electron in the states of the conduction band bottom and hole in the 4f ground state of the Ce³⁺ ion.     

Luminescence properties of Li6GdB3O9:Ce crystal fibers upon their excitation in the range of 4d → 4f core transitions

We have investigated UV luminescence with a subnanosecond time resolution of Li₆GdB₃O₉:Ce crystal fibers upon their ultrasoft X-ray selective excitation at 10 and 293 K in the range of 4d → 4f core transitions. We have revealed an intense fast-decaying subnanosecond luminescence component, which is caused by a high local density of electronic excitation and Auger core hole relaxation processes, and modulation of the luminescence excitation spectrum by an absorption band of the 4d–4f photoionization giant resonance in the energy range 135–160 eV.     

Contrast analysis of Shockley partial dislocations in 4H-SiC observed by synchrotron Berg–Barrett X-ray topography

Shockley partial dislocations in 4H-SiC were observed using monochromatic synchrotron X-ray topography with a grazing-incidence Bragg-case geometry, that is, Berg–Barrett topography. The contrast of partial dislocations at the edges of Shockley-type stacking faults is discussed in terms of whether they have C- or Si-core edge components, or screw components. The dissociated state of basal-plane dislocation is discussed on a basis of the stacking sequence for basal-planes in the 4H-SiC crystal structure. It is expected that the results obtained in this study will be useful for characterizing Shockley-type stacking faults in Berg–Barrett topography.     

The excitation functions of 4s–4p and 3d–4p transitions in Ni atoms sputtered from metallic targets by Ar+ ions

The intensities of spectral lines corresponding to 4s–4p and 3d–4p transitions in Ni atoms sputtered from metallic targets by Ar⁺ ions were measured. The energy of primary ions was varied from 4 KeV to 10 keV. Both single crystal and polycrystalline targets were used at various temperatures including ferromagnetic and paramagnetic phases. The excitation functions calculated from experimental data can be explained only by the assumption that the promotion of the electrons occurs during energetic binary collisions of atomic particles in the solid.     

Photoinduced transformations in (As1–xBix)2S3 glass observed by Raman spectroscopy

Raman spectra of (As_1–xBi_x)₂S₃ glass samples with x ≤ 0.2 measured at the excitation with above-bandgap (532 nm) laser light at a relatively low power density (P_exc = 4 kW/cm²) clearly confirm the amorphous character, thereby markedly extending the known compositional interval of existence of the (As_1–xBi_x)₂S₃ glass previously known (x ≤ 0.06). Spectra measured at an increased P_exc (40 kW/cm²) reveal a photostructural transformation in the illuminated area of the glass leading to an additional contribution of Bi–S bonds as well as to an increasing number of cage-type As₄S₄ units with homopolar As–As bonds. A number of new features in a broad range up to about 1,000 cm⁻¹, which emerge in the Raman spectra of the (As_1–xBi_x)₂S₃ glasses with high (x ≥ 0.14) Bi content and increase in intensity with the exposure time, are related to a photochemical transformation, namely, oxidation of arsenic and sulphur on the (As_1–xBi_x)₂S₃ glass surface with formation of units containing arsenate AsO₄³⁻ and sulphate SO₄²⁻ ions. These processes are irreversible and occur only in the presence of a sufficient amount of bismuth.     

Interconfigurational 5d?→?4f luminescence of Ce(3+) and Pr(3+) in Ca(9)Lu(PO(4))(7)

Ca(9)Lu(PO(4))(7):Ce (3+) and Ca (9)Lu (PO (4))(7):Pr (3+) polycrystalline materials were synthesized by solid state reaction at high temperature. The materials were characterized by powder x-ray diffraction (XRPD). The luminescence spectroscopy and the excited state dynamics of these compounds were investigated upon excitation with UV/VUV synchrotron radiation. Both materials showed efficient and fast 5d-4f emission upon direct VUV excitation into the 5d levels but only Ca(9)Lu(PO(4))(7):Ce (3+) revealed luminescence upon excitation across the bandgap. The decay kinetics of the 5d-4f emission upon VUV intra-center excitation is characterized by a decay time of 29?ns for Ce (3+) and 17 ns for Pr (3+) with no significant build-up after the excitation pulse. For the both compounds, no significant temperature dependence of the 5d-4f emission lifetime was observed within the range 8-300?K.     

Electron paramagnetic resonance and optical spectroscopy of K3Na(CrO4)2 ferroelastics activated by MnO 4 2− molecular impurity ions

Crystals of a proper ferroelastic K₃Na(CrO₄)₂ containing molecular impurity ions MnO ₄ ^2? are studied using electron paramagnetic resonance (EPR) and optical spectroscopy. The EPR spectrum of the Mn⁶⁺ ion contained in the molecular impurity ion MnO ₄ ^2? is identified at low temperatures (T ≤ 20 K). The intensity of this spectrum decreases unusually fast as the temperature increases. A broad IR luminescence band with a vibronic structure well resolved at a temperature of 8 K is revealed. Theoretical treatment of the Mn⁶⁺ ion involved in the molecular impurity ions MnO ₄ ^2? of the K₃Na(CrO₄)₂ ferroelastic crystal suggests that an important role in this case is played by the pseudo-Jahn-Teller. The pseudo-Jahn-Teller effect offers an explanation for the appearance of a fine structure in the vibronic replicas in the luminescence spectrum, on the one hand, and accounts for the fast decrease in the intensity of the EPR spectrum of K₃Na(CrO₄)₂: MnO ₄ ^2? with increasing temperature, on the other.     

Size and morphological effect of Au–Fe3O4 heterostructures on magnetic resonance imaging

In this paper, we analyse the melting of a spherically symmetric nanoparticle, using a continuum model which is valid down to a few nanometres. Melting point depression is accounted for by a generalised Gibbs–Thomson relation. The system of governing equations involves heat equations in the liquid and solid, a Stefan condition to determine the position of the melt boundary and the Gibbs-Thomson equation. This system is simplified systematically to a pair of first-order ordinary differential equations. Comparison with the solution of the full system shows excellent agreement. The reduced system highlights the effects that dominate the melting process and specifically that rapid melting is expected in the final stages, as the radius tends to zero. The results agree qualitatively with limited available experimental data.     

NⅡ离子2p4f—2p3d辐射跃迁概率的理论研究

在全相对论理论框架下，利用多组态Dirac-Fock(MCDF)方法，系统计算了NⅡ离子2p4f—2p3d的辐射跃迁概率，得到的结果与已有实验值符合很好.具体计算中，详细分析了相对论效应、电子关联、弛豫效应、Breit相互作用和量子电动力学(QED)效应对能级精细结构及辐射跃迁概率的影响.结果表明：相对论效应、电子关联和弛豫效应对NⅡ 2p4f-2p3d辐射跃迁概率有很重要的影响,考虑了这些效应后计算值得到明显改善.     

Cu2ZnSnSe4 films by selenization of Sn–Zn–Cu sequential films

This paper deals with the formation of Cu₂ZnSnSe₄ (CZTS) in the process of selenization of metal precursor layers in elemental selenium vapour. Metallic precursors were sequentially evaported from Sn, Zn and Cu sources. Precursor Sn–Zn–Cu films have a “mesa-like” structure and consist mainly of Cu₅Zn₈ and Cu₆Sn₅ phases. It was confirmed that the formation of different binary copper selenides is the dominating process of selenization in elemental Se vapour at temperatures up to 300 °C. The formation of kesterite CZTS films begins at 300 °C and dominates at higher temperatures, always resulting in multiphase films that consist of high-quality Cu₂ZnSnSe₄ crystals and of a separate phase of ZnSe.     

Analysis of the Coriolis interaction between ν6 and ν4 bands of ethylene-cis-d2(cis-C2H2D2) by high-resolution FTIR spectroscopy

The Fourier transform infrared (FTIR) spectrum of the ν₆ band of ethylene-cis-d₂(cis-C₂H₂D₂) was recorded with a unapodized resolution of 0.0063 cm^?1 in the 990–1100 cm^?1 region. A total of 609 transitions were assigned to this band centred at 1039.7682 ± 0.0003 cm^?1. The ν₆ band was found to be coupled to the ν₄ band by a-type Coriolis resonance. Both perturbed and unperturbed transitions were assigned and fitted to give eight rovibrational constants with high accuracy for the v₆ = 1 state with a standard deviation of 0.00097 cm^?1 using a Watson’s A-reduced Hamiltonian in the I^r representation. From a rovibrational analysis of the Coriolis interaction between the ν₆ band and non-infrared active ν₄ band of cis-C₂H₂D₂, the band centre of ν₄ at 984.9 ± 0.2 cm^?1 was derived. Furthermore, the second-order a-type Coriolis coupling constant between the two bands was obtained for the first time.