X-ray L1, L2 and L3 absorption limits of 4D transition metals

The wavelengths and energies of the L₁, L₂ and L₃ absorption limits in Zr, Nb, Ru, Rh, Pd and Ag metals have been measured and some of the previous reported values have been found to be incorrect. By comparing the energies of the absorption limits with those of the Lγ₁Ly, and Lβ_2,15, lines and also with the binding energies obtained by XPS, the electronic transitions corresponding to the respective absorption limits have been clarified. It is concluded that (i) the end level of the electronic transition corresponding to the L₁ absorption limit of Zr-Ag is the 5p-like level, and (ii) the end level corresponding to either of the L₂ and L₃, absorption limits of Zr-Pd is the 4d level, while that of Ag is, rather unexpectedly, the top of the 5s level.     

Oscillator strength of electron-type color centers in KCl single crystals irradiated with electrons and protons

The absorption spectra of KCl single crystals irradiated with electrons and protons at energies of 15 and 100 keV and a particle flux ranging from 5×10¹² to 10¹⁵ cm^?2 are investigated. The absorption bands attributed to simple (F, F _a, K) and complex (M, R ₂, R ₄, N) color centers are identified in the spectra. The correlation dependences of the absorption coefficients for M, R ₂, and R ₄ centers on the absorption coefficient of F centers and the correlation dependences of the absorption coefficients for R ₂ and R ₄ centers on the absorption coefficient of M centers are established. The oscillator strengths are calculated for M, R ₂, and R ₄ color centers.     

Electronic band structure and optical absorption of nanotubular zinc oxide doped with Iron, Cobalt, or Copper

The absorption spectra of the precursor-derived solid solutions Zn_{1 ? x} M _x O (M = Fe, Co, Cu) with a tubular morphology of aggregates have been investigated in the ultraviolet and visible regions. The maximum metal concentration x in the Zn_{1 ? x} M _x O solid solutions is 0.075 for iron, 0.2 for cobalt, and 0.1 for copper. It has been found that the optical absorption and the band gap of the Zn_{1 ? x} M _x O compounds depend on the type of dopant. The obtained experimental data have been interpreted using the results of the performed ab initio calculations of the electronic band structure and optical absorption.     

Double discontinuities of wide separation in the X-ray absorption spectra of transition elements in highly oxidized compounds

The paper consists of two parts. (1) The author studied the mechanism of the appearance of the double discontinuities of wide separation in the X-ray L₁ absorption spectrum of Mo in MoO₃, which were found in the recent research about the effects of chemical combination on various X-ray absorption limits, and that of Nb in Nb₂O₅. Then he arrived at the conclusion that the discontinuity of the higher energy corresponds to the electronic transition from L₁ to 5p, and that of the lower energy is attributed to that from L₁ to the 4d, 5s state. (2) The author applied the explanation to the double discontinuities which have been observed by many researchers in the K absorption spectra of 3d transition elements in highly oxidized compounds, and showed that these double absorption discontinuities are ascribed to the electronic transitions K?4p and K ? 3d, 4s.     

Lβ2 satellites in the X‐ray emission spectra of elements 72Hf, 73Ta, 74W, 81Tl, 83Bi and 92U

The satellite spectra arising due to the L₃M_x–M_xN_4,5 (x = 1–5) transition array in the X‐ray emission spectra of ₇₂Hf, ₇₃Ta, ₇₄W, ₈₁Tl, ₈₃Bi and ₉₂U have been calculated using available HFS data on K–LM and L–MN Auger transition energies. The agreement between the calculated and measured energies, that between calculated and measured separations in energies and the consideration of the relative probabilities of all the L₃M_x–M_xN_4,5 transitions have been used as the basis for deciding the origin of the satellites. It has been established that two satellites observed in the Lβ₂ region of the X‐ray spectra of various elements, named β₂^I and β₂^II in the order of increasing energy, are mainly emitted by the L₃M_4,5–M_4,5N_4,5 transitions. It is observed that satellite β₂^I in the spectra of elements with ₇₂Hf to ₇₄W has been assigned to the superposition of the ³F₄–³G₅ and ³F₄–³D₃ transitions and must be the most intense one among all these satellites. The same transition has been proved to be the main origin of satellite β₂^II, reported in the element with ₈₁Tl, ₈₃Bi and ₉₂U. Further, satellite β₂^I, reported in the spectra of elements with ₈₁Tl and ₉₂U, has been associated with the transitions ³D₃–³F₄ and ¹D₂–¹F₃. Finally, line β₂^II, reported in the spectra of elements with Z = 72–74, has been assigned to the ¹F₃–¹G₄ and ³P₀–³D₁ transitions. The possible contributions of other transitions of the L₃M_x–M_xN_4,5 (x = 1–5) array having intensities comparable with those of the above transitions, as well as the corresponding lines that have not yet been observed, have also been discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

The shape and extended fine structure of the manganese K X-ray absorption discontinuity in its oxides

The shape and extended fine structure of the manganese K absorption discontinuity have been studied in the pure metal and in its four oxides. viz. MnO, Mn₃O₄, Mn₂O₃ ad MnO₂ using a bent crystal Cauchois type spectrograph of 40cm diameter. The shape of the main discontinuity for the oxides is discussed on the basis of molecular orbital theory. Our results show a complimentarity between the absorption spectra and the emission spectra obtained earlier by Tsutsumi et al. for some of these oxides. The extended X-ray absorption fine structure (EXAFS) is discussed in the light of the recent proposed by Lytle et al.     

Study of the electronic structure of M(CO)5Cl complexes (M = Mn, Re) using X-ray spectroscopy and density-functional theory

The electronic structure of M(CO)₅Cl metal complexes (M = Mn, Re) has been investigated by X-ray emission spectroscopy. The obtained X-ray emission C Kα, OKα, Cl Kβ₁, MnLα, and MnKβ₅ spectra for Mn(CO)₅Cl and ReLβ₅ spectra for Re(CO)₅Cl have been interpreted on the basis of the quantum-mechanical calculations by the method of density-functional theory, using the Gaussian-98 program. The investigation of Mn(CO)₅Cl and Re(CO)₅Cl showed similarity of the electronic structure of both complexes. Only small differences have been revealed in the energy structure and orbital occupancies of the atomic orbitals of the corresponding molecular orbitals; these differences are caused by the difference of the type of metal ions and the molecule geometry. On the basis of the performed quantum-mechanical calculations, theoretical X-ray emission spectra have been constructed, which reproduce well the characteristic features of the corresponding experimental spectra of M(CO)₅Cl metal complexes (M = Mn, Re).     

An electronic structure study of europium chalcogenides by soft x-ray spectroscopy

The M_V, M_IV and M_III X-ray emission and absorption spectra of EuO and EuS have been studied. The relative positions and the widths of 4f states and valence or conduction distributions have been deduced from these spectra. These data are compared with those obtained by u.v. photoemission and the results of band structure calculations.     

Search for a new light gauge boson in π0, η and η′ decays

Upper limits for the production of new light gauge bosons in π⁰, η and η′ decays have been obtained with the Crystal Barrel detector. The kinematically well-constrained reactions p?p → π⁰π⁰ P have been studied, where P ? π ⁰, η, η′ decays through the emission of a single photon recoiling against a missing state X. X can be a long-lived weakly interacting particle or it decays into ???. The resulting branching ratio upper limits (90 % C.L.) are: 6 × 10^?5 for masses M _X of the missing particle X lying between 65 MeV/c² and 125 MeV/c² (π⁰ decay), 6 × 10^?5 for M _X between 200 MeV/c² and 525 MeV/c² (gh decay), and 4 × 10^?5 for M _X between 50 MeV/c² and 925 MeV/c² (η′ decay). The π⁰-decay limit represents an improvement by a factor of 4 to 8 (depending on M _X) when compared to the existing limit, whereas the η and η′ decay limits have been measured for the first time, thereby extending the M _X range from 125 MeV/c² up to 925 MeV/c².     

Vapour phase M4,5N4,5N4,5 Auger electron spectra of antimony and tellurium

High resolution M_4,5N_4,5N_4,5 Auger electron spectra from Sb₄ and Te₂ vapours have been measured using electron impact excitation. The spectra have been decomposed into line components and relative intensities and energies of the components are compared with calculated intensities and energies. The calculations have been done for these molecular samples using the free-atom calculation model involving initially filled shells. The calculations have been treated in the mixed coupling scheme using jj coupling for initial state and intermediate coupling for the final state. The experimental results agree well with the calculated values, indicating that the molecular effects on the relative intensities and energies are very small for these core level transitions. The clear molecular effects are found in the broadening of lines and in the kinetic energy shifts due to extra-atomic relaxation effects.     

Ionization energies and optical spectra of 5d-metal hexafluorides as calculated in the Dirac-Slater model

A relativistic self-consistent Dirac-Slater model has been used in a study of the electronic structure of 5d-metal hexafluorides. Experimental absorption spectra have been compared with calculated energies obtained as one-electron energy differences. The calculated “crystal field” splitting between the relativistic analog oft _2g ande _g levels, as well as spinorbit splitting of thet _2g level, has been found to be in good agreement with experimental data. Ionization energies which agree well with available spectra have been calculated using a transition state procedure. From a Mulliken population analysis of the molecular levels and ground state charge densities the validity of the classical crystal-field model is discussed.     

High resolutionMNN auger spectra of Ag,Cd, In,Sb, Te,and I

The strongest lines (M ₅ N _4,5 N _4,5 andM ₄ N _4,5 N _4,5) in theMNN Auger spectra of Ag, Cd, In, Sb, Te, and I have been investigated with high resolution by means of an electrostatic cylindrical spectrometer. The measured spectra have been found to have a fine structure corresponding to the splitting of the final states of the Auger transitionsM ₅ N _4,5 N _4,5 andM ₄ N _4,5 N _4,5. This has not been observed for these elements in spectra measured by the retarding field method. The line profiles are discussed.     

Study of L2,3M4,5M4,5 Auger spectra of Zn and Cu in molecular ZnCl2 and (CuCl)3 vapours

L_2,3M_4,5M_4,5 Auger electron spectra of Zn and Cu have been measured in molecular ZnCl₂ and (CuCl) ₃ vapours. The spectra have been analyzed and compared with the corresponding free-atom spectra. It is found that the main features of the spectra are atomic-like. The energies are shifted by 0.55 eV in ZnCl₂ and by 3.2 eV in (CuCl)₃ towards higher kinetic energy compared with the corresponding free-atom spectra. For the intensity ratios between the L₃ and L₂ groups, the values 2.8 and 3.7 are obtained for Zn and Cu, respectively. These intensity ratio, together with energy considerations based on free-atom Dirac—Fock calculations and observed Auger shifts, indicate that the L₂L₃M_4,5 Coster—Kronig process is energetically possible in (CuCl)₃ molecular clusters but not in ZnCl₂. The satellite structure in the spectra studied also supports this conclusion.     

DSC, TGA and dielectric properties of carboxymethyl cellulose/polyvinyl alcohol blends

Films with different compositions of polyvinyl alcohol (PVA) and carboxymethyl cellulose (CMC) blends have been prepared using the casting method. Differential scanning calorimetery (DSC), thermogravimetric analysis (TGA) and dielectric spectroscopy of all compositions have been investigated. It was found that PVA and CMC are compatible in the studied range of composition. With increasing CMC content, the thermal stability of PVA increases. Based on DSC and TGA data, the activation energies of all the investigated samples were calculated. The absorption edge (E_a) was also determined from Ultraviolet-visible (UV-vis) spectra.Dielectric permittivity, loss tangent and ac conductivity of all samples were studied as functions of temperature and frequency. The results show that the dielectric dispersion consists of both dipolar and interfacial polarization. The frequency dependence of the ac conductivity indicates that the correlated barrier hopping (CBH) is the most suitable mechanism for conduction. The polaron binding energy (U_M) was determined. Results of the present system are compared with those of similar materials.     

Characterisation of thin films of bismuth oxide by X-ray photoelectron spectroscopy

The XPS (or ESCA) technique has been used for the characterisation of vacuum-deposited thin films of bismuth oxide. The spectra of Bi metal and Bi₂O₃ powder are used for comparison. The characterisation is carried out by consideration of the positions of the Bi 4f_{$\text{7}\text{2}$} and 4f_{$\text{5}\text{2}$} peaks and by using peak-fitting routines. A lower suboxide of bismuth, and metallic bismuth are observed in bismuth oxide films as evaporated. Oxidation of these films by heating in air results in bismuth(III) oxide. A linear relation is found between the binding energies and oxidation state. The corresponding O 1s spectra for the two types of film are also discussed.     

Gamma-gamma directional correlations in the decay of206Po

Directional correlations of gamma-gamma cascades in the decay of²⁰⁶Po have been measured for the first time. Using a multichannel goniometer with 2 Ge(Li) and 6 NaI(Tl) detectors theA ₂ andA ₄ coefficients have been measured for five cascades in²⁰⁶Bi. From the results,E2/M1 mixing ratios of nine transitions are determined. Upper limits of the transition strengths are presented. Three of the measured mixing ratios are compared with theoretical estimates based on magnetic dipole and electric quadrupole moments of neighbouring nuclei.     

Proprietes electriques des phases de basse temperature M1, T et M2 dans VO2 dope au chrome et a l'aluminium

The electrical conductivity and thermopower have been measured on Cr and Al doped VO₂ single crystals. The insulating M₁, T and M₂ phases have a similar behaviour with an activation energy E_a ?0.40 eV. The conductivity halves abruptly at the T→M₂ transition but no discontinuity is observed for the thermopower. The ansiotropy of the thermopower may be due to the anisotropic mobility of the holes in the lower quasi one dimensional Hubbard band.     

Relaxation energies for photoionization of tellurium

The energies of the 3p, 3d, 4s, 4d, 5s and 5p photopeaks and of the M_{4, 5}NN and M_{4, 5}NO Auger peaks have been measured for tellurium metal. The associated relaxation energies were computed by two different methods, first, by comparing the measured binding energies with those calculated theoretically employing Koopman's theorem, and second, by a method devised by Shirley and co-workers. The merits of these two methods are examined by comparing measured MNN, MNO and KLL Auger energies with those calculated using the predicted relaxation energies.     

Vibrational spectra of M3PCr4O16 (M = K,NH4)

The infrared and Raman spectra of the two phosphochromates M₃PCr₄O₁₆ (M = K, NH₄) have been recorded and analysed. The spectra could be interpreted on the basis of the vibrations of Cr-O-P, O-P-O and CrO₃ groups. A large number of vibrational bands have been observed for each mode due to the existence of different Cr-O bond lengths. The anion is more distorted in potassium phosphochromate. The three ammonium groups are distinct.     

Fully relativistic analysis of the covalence effects for the isoelectronic 3d ions (Cr, Mn, Fe) in SrTiO3

Fully relativistic calculations of the energy levels, absorption spectra, molecular orbitals (MO) compositions, covalence effects and energies of the charge transfer (CT) transitions for three isoelectronic ions Cr³⁺, Mn⁴⁺, Fe⁵⁺ in the SrTiO₃ (STO) crystal have been performed. The recently developed first-principles approach to the analysis of the absorption spectra based on the first principles discrete variational multi-electron method (DV-ME) (K. Ogasawara et al., Phys. Rev. B 64 (2001) 115413) was used in the calculations. As a result, energy levels of the above ions, their absorption spectra and energies of the lowest CT transitions were all calculated. By performing analysis of the MO population, it was shown that the degree of covalence of the chemical bonds between 3d ions and oxygen ions in SrTiO₃ increases in the following order: Cr³⁺→Mn⁴⁺→Fe⁵⁺, whereas the CT energies monotonically decrease in the same order.