Electronic Absorption Spectra of 2-Fluoro-4-bromo, 4-Fluoro-2-bromo and 2-Fluoro-5-bromo Toluenes

Abstract

Absorption spectra of 2-Fluoro-4-Bromo, 4-Fluoro-2-Bromo and 2-Fluoro-5-Bromo Toluenes have been investigated in the near ultraviolet region in vapour phase. The band systems correspond to allowed transitions with the most intense bands at 2742.09 Å (36458 cm^?1), 2745.96 Å (36406 cm^?1) and 2771.74 Å (36068 cm^?1) identified as 0,0 transitions in 2-Fluoro-4-Bromo, 4-Fluoro-2-Bromo and 2-Fluoro-5-Bromo Toluenes respectively. The bands in 4-Fluoro-2-Bromo Toluene have been analysed in terms of the ground state fundamental 208 cm^?1 and excited state fundamentals 244, 611, 855 and 1211 cm^?1 and the bands in 2-Fluoro-4-Bromo and 2-Fluoro-5-Bromo Toluenes are explained in terms of the upper state fundamentals 716, 987 and 1230 cm^?1 and 722, 886 and 2130 cm^?1 respectively.     

Absorption of Dy3+ and Nd3+ ions in BaR 2F8 single crystals

The Dy³⁺ absorption and excitation spectra of BaY₂F₈ and BaYb₂F₈ single crystals are investigated in the ultraviolet, vacuum ultraviolet, and visible ranges at a temperature of 300 K. These crystals exhibit intense broad absorption bands due to the spin-allowed 4f-5d transitions in the range (56–78) × 10^?3 cm^?1 and less intense absorption bands that correspond to the spin-forbidden transitions in the range (50–56) × 10^?3 cm^?1. The Nd³⁺ absorption spectra of BaY₂F₈ single crystals are studied in the range (34–82) × 10^?3 cm^?1 at 300 K for different crystal orientations.     

Excitation and Emission Spectra of Cs2NaLnCl6 Crystals Using Synchrotron Radiation

ABSTRACT

The visible emission and vacuum ultraviolet excitation spectra of the series Cs₂NaLnCl₆ (Ln = Y, Nd, Sm, Eu, Tb, Er, Yb) and Cs₂NaYCl₆:Ln³⁺ (Ln = Sm, Er) have been recorded using synchrotron radiation at room temperature, and in some cases at 10 K. The excitation spectra comprise features associated with charge transfer, excitation from the valence to conduction band, and impurity bands. No d–f emissions were observed for these Ln³⁺ ions, so that the emission bands comprise intraconfigurational 4f ^N –4f ^N transitions and impurity bands, whose natures are discussed. Theoretical simulations of the f–d absorption spectra have been included. The comparison with data from the synchrotron at Desy enables a comprehensive account of the ground (or vibrationally excited ground for Ln²⁺) states of the Ln³⁺ 4f ^N , Ln³⁺ 4f ^N?15d, and Ln²⁺ 4f ^N+1 configurations relative to the valence and conduction bands of Cs₂NaLnCl₆, for which the band gaps are between 6.6 and 8.1 eV.     

Absolute oscillator strengths of 5f-5f transitions of U4+ in ThBr4 and in hydrobromic acid solutions

Absolute oscillator strengths of 5f² transitions of U⁴⁺ in ThBr₄ and in hydrobromic acid solutions are found to be about 10^-4 which is two orders of magnitude larger than those for 4f-4f transitions (lanthanide series) and one order of magnitude larger than 5f³ ones (U³⁺). Applicability of Judd's theory to 5f² transitions is discussed with particular attention to the roles played by reduced matrix elements of odd rank tensor U^λ and by the proximity of the 6d configuration.     

Intra- and inter-configurational luminescence spectroscopy of Pr3+ -doped YPO4 nanophosphors

Nanopowders of YPO₄ phosphors with different Pr³⁺doping were successfully prepared by a sol gel method under different synthesis conditions. The crystallite size and strain show a strong dependence on the Pr³⁺ doping concentration and on the annealing temperature. By annealing at 300 °C one can obtain the xenotime structure of the pure YPO₄. The crystallite size can be controlled by controlling the annealing temperature and it increases with increasing the annealing temperature. The room temperature inter-configurational 4f² ↔ 4f5d and intra-configurational 4f²↔ 4f² emission-excitation transitions spectra are measured and investigated. Upon 4f² → 4f5d excitation transition, all the samples present broad intense emission bands attributed to 4f5d → 4f² emission transitions and peaks in red region assigned to ¹D₂→³H₄ transition as photon cascade emission phenomena (PCE). The presence of only ¹D₂→³H₄ transition is discussed. In addition, the ¹D₂ energy level lifetimes as well as the refractive indexes were determined and discussed.     

Levels in 156Gd studied in the (n, γ) reaction

Levels up to 2.3 MeV in ¹⁵⁶Gd have been studied using the (n, γ) reaction. Energies and intensities of low-energy γ-rays and electrons emitted after thermal neutron capture have been measured with a curved-crystal spectrometer, Ge(Li) detectors and a magnetic electron spectrometer. High-energy (primary) γ-rays and electrons have been measured with Ge(Li) detectors and a magnetic spectrometer. The high-energy γ-ray spectrum has also been measured in thermal neutron capture in 2 keV resonance neutron capture. The neutron separation energy in ¹⁵⁶Gd was measured as S_n = 8535.8 ± 0.5 keV.About 600 transitions were observed of which ~50% could be placed in a level scheme containing more than 50 levels up to 2.3 MeV excitation energy. 42 of these levels were grouped into 15 excited bands. In addition to the β-band at 1050 keV we observe 0⁺ bands at 1168, 1715 and 1851 keV. Other positive-parity bands are: 1⁺ bands at 1966, 2027 and 2187 keV; 2⁺ bands at 1154 (γ-band) and 1828 keV; and 4⁺ bands at 1511 and 1861 keV. Negative-parity bands are observed at 1243 keV (1^?), 1366 keV (0^?), 1780 keV (2^?) and 2045 keV (4^?). Reduced E2 and E0 transition probabilities have been derived for many transitions. The ground band, the β- and γ-bands and the 0⁺ band at 1168 keV have been included in a phenomenological four-band mixing calculation, which reproduces well the experimental energies and E2 transition probabilities.The lowest three negative-parity (octupole) bands of which the 0^? and the 1^? bands are very strongly mixed, were included in a Coriolis-coupling analysis, which reproduces well the observed energies. The E1 transition probabilities to the ground band are also well reproduced, while those from the higher-lying 0⁺ bands to the octupole bands are not reproduced. Absolute and relative transition probabilities have been compared with predictions of the IBA model and the pairingplus-quadrupole model. Both models reproduce well the E2 transitions from the γ-band, while strong disagreements are found for the E2 transitions from the β-band. The IBA model predicts part of the decay features of the higher lying 2⁺₂, 4⁺₁ and 2^?₁ bands.     

Transition energy and dipole oscillator strength of 1s23d-1s2 nf transitions for Sc18+ ion

The transition energies of the 1s²3d-1s² nf (4?n?9) transitions and fine structure splittings of 1s² nf (n?9) states for Sc¹⁸⁺ ion are calculated with the full-core plus correlation method. The quantum defect of 1s² nf series is determined by the single-channel quantum defect theory. The energies of any highly excited states with n?10 for this series can be reliably predicted using the quantum defect as function of energy. Three alternative forms of the dipole oscillator strengths for the 1s²3d-1s² nf (n?9) transitions of Sc¹⁸⁺ ion are calculated with the transition energies and wave functions obtained above. Combining the quantum defect theory with the discrete oscillator strengths, the discrete oscillator strengths for 1s²3d-1s² nf (n > 9) transitions and the oscillator strengths densities corresponding to the bound-free transitions are obtained.     

Site selective 4f5d spectroscopy of CaF2 : Pr

Spectroscopic investigations were performed on a single crystal of CaF₂ doped with 0.05% Pr³⁺. Three different Pr³⁺ sites with different luminescent properties were identified. The 4f² →4f¹5d¹ excitation spectrum of the first site has a sharp maximum at 221.3 nm. Excitation in the 4f5d bands of this site yields strong 4f5d emissions in the UV/VIS part of the spectrum and also weaker intraconfigurational 4f² emissions. By comparing the intraconfigurational 4f emissions and their decay times with data from the literature, these 4f5d bands are assigned to transitions on Pr³⁺ ions on a site with C_4V symmetry. The fd excitation spectrum of the second site has a zero phonon line at 223.3 nm. Upon selective excitation in this band, only 4f5d emission is observed. Probably, these 4f5d bands correspond to Pr³⁺ ions on a O_h site. The third set of 4f5d bands has a 4f5d onset at 208 nm. By comparison of the luminescence spectra of the intraconfigurational 4f² transitions with literature data, these transitions are assigned to Pr³⁺ on an L site. Excitation in these 4f5d band yields ¹S₀ emission followed by emission from the ³P₀ state. The present results clarify some contradictions reported in the literature.     

Step-wise laser excitation of the 4snf 3F Rydberg states of neutral zinc

The new experimental results on the effective quantum numbers and term energies of the highly excited odd-parity 4s4d ³D_1,2,3 →4snf ³F_2,3,4 Rydberg transitions of zinc have been presented. The experiment was performed using the three dye lasers simultaneously pumped by the second harmonic (532?nm) of the Q-switched Nd:YAG laser. The new observation includes the 4snf ³F₃ (12?≤n?≤?50) series excited from the 4s4d ³D₂ intermediate level. In addition, the 4snf ³F₂ (12?≤n?≤?28) and 4snf³F₄ (12?≤n?≤?33) series are observed from the thermally populated 4s4d ³D_1,3 fine structure components. The ionization potential of zinc has been determined from the unperturbed 4snf ³F₃ series as 75769.31?±?0.15?cm^?1, which is in excellent agreement with the previously reported value.     

Soft X-ray bands of highly ionized tungsten,gold and lead emitted by the TEXT tokamak plasma

Spectra of highly ionized tungsten, gold and lead emitted from the TEXT tokamak have been recorded in the 20–70 Å range by means of a grazing incidence, time-resolving spectrograph. The narrow and bright emission bands centered around 40, 45 and 50 Å in Pb, Au and W respectively, and bands of lesser intensities at lower wavelenghts, are emitted by a very large number of superimposed lines originating from transitions of the type 4d¹⁰4fⁿ−4d⁹4fⁿ⁺¹, 4d¹⁰4fⁿ−4d⁹4fⁿ5p and 4fⁿ−4fⁿ⁻¹5l (l=d, g). The isoelectronic analysis shows that at the electron temperatures prevailing in the present experiment, T_e≈800 eV, there are no contributions to the bands from ions having a 4p⁶4dⁿ ground state. This, together with the experimental measurement of the electron temperature profile, indicates that the heavy ion impurity distribution in the tokamak plasma is very close to ionization equilibrium.     

Reflectivity of Tm monochalcogenides: No evidence of valence fluctuations

The reflectivity of metallic TmS, TmSe and semiconducting TmTe has been measured between 0.03 eV and 12 eV and has been interpreted as 4fⁿ-4f^n?15d and p-d interband transitions and coupled plasmon modes.     

Tuning Photophysical and Electrochemical Properties of Phosphorescent Heteroleptic Iridium Complex Salts–as Chemosensors

Photophysical and electrochemical studies of cyclometalated cationic heteroleptic iridium(III) complex salts have been carried out. For these complex salts the intense absorption bands appeared around 263 nm and are assigned to spin-allowed π-π* transitions of phenanthroline ligands. Moderately intense and weak absorption bands observed around 341 and 440 nm, respectively. These bands are assigned to spin-allowed metal to ligand charge transfer ¹MLCT and ³MLCT transitions, respectively. The influence of anions and proton on the photophysical and electrochemical studies were also carried out. The emission wavelength was red shifted and emission color changed from yellow to red by the addition of CF₃CO₂H. The solution color changed from green to brown and the emission was quenched by the addition anions such as of F^?, CH₃COO^? and H₂PO₄ ^?.     

Term structure of 4d-electron configurations and calculated spectrum in Sn-isonuclear sequence

Theoretical calculations of term structure are carried out for the ground configurations 4d^w, of atomic ions in the Sn isonuclear sequence. Atomic computations are performed to give a detailed account of the transitions in Sn⁺⁶ to Sn⁺¹³ ions. The spectrum is calculated for the most important excited configurations 4p⁵ 4dⁿ⁺¹, 4dⁿ⁻¹ 4f¹, and 4dⁿ⁻¹ 5p¹ with respect to the ground configuration 4dⁿ, with n=8-1, respectively. The importance of 4p-4d, 4d-4f, and 4d-5p transitions is stressed, as well as the need for the configuration-interaction CI treatment of the Δn=0 transitions. In the region of importance for extreme ultraviolet (EUV) lithography around 13.4 nm, the strongest lines were expected to be 4dⁿ-4p⁵ 4dⁿ⁺¹ and 4dⁿ-4dⁿ⁻¹ 4f¹.     

Model-potential oscillator strengths for 4fn6s2–4fn6s6p transitions in Sm(I), Eu(I), Dy(I), Er(I) and Yb(I)

The 4fⁿ6s²?4fⁿ6s6p transitions are studied for neutral samarium, europium, dysprosium, erbium, and ytterbium. Four different couplings between the valence electrons and the 4fⁿ shell are considered, three are based on the LS and one on the J_IJ_II scheme. The radial integrals are computed with the model-potential method, which includes both exchange and core polarization. The results are compared with those obtained by employing the Coulomb approximation and the ab initio Hartree + Exchange (HX) approach, as well as with available experimental data. The core-polarization influence on oscillator strengths for these transitions is also investigated.     

Spectral Study of Some Samarium Complexes in the Region 750–250 cm−1

Abstract

Rare earth β -diketonates and diketo-ester complexes are promising laser materials due to narrow line width of the internal 4fⁿ transitions and weak crystal-field interactions¹. The electronic energy states², spectral intensities^3–5, bonding^6,7 and infrared spectra^8–11 of some of these complexes have been recently reported by the authors. However, little information regarding their structure and strengths of various bonds are available. The infrared spectra of rare earth complexes in the spectral region 4000 – 750 cm^?1 are characteristic of the ligand, while those in the region 750 – 250 cm^?1 characterize the metal-ligand bonding. The present communication reports the values of force constants computed from the observed infrared absorption spectra of four ethyl 1-methyl acetoacetate (EMA) and ethylbenzoylacetate (EBA) complexes of trivalent samarium in the region 750 – 250 cm^?1.     

Luminescence characteristics of the Pr<Superscript>3+</Superscript> ion in SrB<Subscript>4</Subscript>O<Subscript>7</Subscript> and SrB<Subscript>6</Subscript>O<Subscript>10</Subscript>

Spectral and kinetic characteristics of the luminescence and luminescence excitation spectra of polycrystalline SrB₄O₇:Pr (1%) and SrB₆O₁₀:Pr (1%) samples are studied at 150–170 K. The samples show an intense luminescence band in the vicinity of 405 nm (¹ S ₀→¹ I ₆ transitions of Pr³⁺) and shorter wavelength bands also assigned to transitions from the ¹ S ₀ level. The main luminescence decay constant is ～2×10^?7 s. The excitation spectra of the ¹ S ₀ luminescence in these crystals are significantly different. The SrB₄O₇:Pr crystal shows three well-resolved bands at 6.14, 6.55, and 6.91 eV in the region of the 4f ²→4f ¹5d transitions and a complex structure in the region of interband transitions (7.1–20 eV), whereas the SrB₆O₁₀:Pr crystal shows a weakly structured band at 6.31 eV and no excitation in the region of the interband transitions. The physical mechanisms that may be responsible for the observed features of the spectra are discussed.     

Infrared Spectra of Morfolonium (mpH)2Mo2Cl6(H20)2(I),(mpH)2Mo2ClxBr6-x(H2O)2(II)/ (mpH)2Mo2Br6(H2O)2(III) and the Pyridinium (PyH)2Mo2I6(H2O)2(IV)Hexahalo-di(aquo): dimolybdate(II) Complexes,Containing Quadruple Metal-Metal Bounds

Abstract

The electronic (800–400 nm), infrared (4000–200,400–20 cm^?1), ordinary Raman (400–200 cm^?1) spectra of morpholinium and the pyridium hexahalo-di(aquo) dimolybdate(II) complexes, containing quadruple metal-metal bonds were investigated. The electronic spectra of the solid compounds at various temperatures (25,100 and 300K) demonstrate intense and structured bands in the visible region (510–582 nm) attributed to the expected δ→δ? transitions.

From the infrared and Raman spectra, the skeletal stretching modes in these complexes have been localized, and the charectenstic bands of these ions were observed in the expected regions.

Finally, the ionic interections were relatively weak, but the existance of phenomena was perceptible and the result was obtained in agreement with X-ray data.     

Fine-structure splittings of 2F states of singly ionized strontium

We have studied the 4d?nf and 5d?nf (n = 4?8) transitions of singly ionized strontium using high-resolution optical spectroscopy. The ²F fine structure is inverted in all the states observed and decreases from ?1.06cm^?1 in 4f to ?0.26 cm^?1 in 8f.     

VUV-luminescence and excitation spectra of the heavy trivalent rare-earth ions in fluoride matrices

VUV 4f ⁿ → 4f^n?15d transitions of Gd³⁺, Er³⁺, Tm³⁺, and Lu³⁺ in fluoride matrices have been analyzed with high-resolution luminescence and excitation spectroscopy. In trifluorides, strong electron-phonon coupling has been found. In the other matrices, the luminescence spectra clearly yield zero-phonon lines and phonon replica, indicating intermediate coupling. The energies of the zero-phonon lines observed are compared with theoretical predictions. Near the threshold of f → d excitations, some of the excitation spectra yield sharp structures which cannot be explained with phonon replica but will be discussed in terms of the energy levels of the 4f^n?15d configuration.     

Intensity and bandwidth of multiphonon vibronic transitions of rare-earth ions in crystals

The theory of multiphonon vibronic coupling to electronic transitions is applied in analysing fluorescence spectra of Eu²⁺ in BaFCI, which consist of the 4f⁷(⁶P_7/2,) → 4f⁷(⁸S_7/2) and 4f⁶5d → 4f⁷ transitions, and the 4f⁷-4f⁶5d excitation spectrum of Ce³⁺ in YPO⁴. The 4f electrons are weakly coupled to lattice vibration modes so that only weak one- and two-phonon sidebands are observable in the 4f-4f optical transitions, whereas the electron-phonon coupling is significantly stronger for a 5d electron. Accordingly, intensive multiphonon vibronic transitions overwhelmingly dominate the 4f⁶5d → 4f⁷ spectrum. It is shown that the extended Judd-Ofelt theory for weak vibronic coupling in the framework of the M-process is equivalent to the Huang-Rhys theory for the δ-process. In the analysis of experimental data, contributions from local ligand modes and lattice acoustic modes are separated, and the coupling strength is evaluated, in terms of the Huang-Rhys parameter S, for the 4f-4f and 5d-4f vibronic transitions.