Relative internal conversion electron intensities of the 113 keV transition in177Hf

The intensities of the internal conversion lines of the 113 keVM1 +E2 transition in¹⁷⁷Hf have been measured. From comparison with theoretical conversion coefficients the transition has been found to be (95.2 ± 0.5)%E2 corresponding to ¦δ¦=4.5 ± 0.3. The theoreticalL _I andM _I conversion coefficients used in the comparison have been increased by 5% according to the result that for pureE2 transitions in the deformed region theL _I/L _II,L _I/L _III,M _I/M _II, andM _I/M _III theoretical ratios are too low (～5%). Moreover, the present result indicates that theL _II/L _III andM _II/M _III ratios obtained from the tabulations by Hager and Seltzer and from the computer program by Pauli are too high (1–2%).     

High resolution lmm auger electron spectra of some first row transition elements

Auger spectra have been recorded from elements of the first transition series using a hemispherical analyser. Highly resolved LMM spectra were obtained showing for the first time the composite nature of these peaks for many of the elements studied. The recorded spectra show a general similarity for the elements Sc → Zn but interesting differences emerge. At the beginning of the transition period the L₃ based transitions have the relative intensities L₃ M_2,3, M_2,3 > L₃ M_2,3, M_4,5<> L₃ M_4,5, M_4,5 whereas towards the end of the series the order L₃ M_4,5, M_4,5 > L₃ M_2,3, M_4,5<> L₃ M_2,3, M_2,3 is observed. Pronounced chemical shifts have been observed upon oxidation. The spectra are interpreted in terms of an L -S coupling scheme and the fine structure discussed in terms of effects produced by multiplet splitting.     

The Studies of Enhanced Fluorescence in the Two Novel Ternary Rare-Earth Complex Systems

Two novel ternary rare-earth complexes SmL₅·L^’·(ClO₄)₂·7H₂O and EuL₅·L^’·(ClO₄)₂·6H₂O (the first ligand L = C₆H₅COCH₂SOCH₂COC₆H₅, the second ligand L^’ = C₆H₄OHCOO⁻) were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, ¹HNMR and UV spectra. The detailed luminescence studies on the rare-earth complexes showed that the ternary rare-earth complexes presented stronger fluorescence intensities, longer lifetimes, and higher fluorescence quantum efficiencies than the binary rare-earth materials. After the introduction of the second ligand salicylic acid group, the relative emission intensities and fluorescence lifetimes of the ternary complexes LnL₅·L^’·(ClO₄)₂·nH₂O (Ln = Sm, Eu; n = 7, 6) enhanced more obviously than the binary complexes LnL₅·(ClO₄)₃·2H₂O. This indicated that the presence of both organic ligand bis(benzoylmethyl) sulfoxide and the second ligand salicylic acid could sensitize fluorescence intensities of rare-earth ions, and the introduction of salicylic acid group was a benefit for the fluorescence properties of the ternary rare-earth complexes. The fluorescence spectra, fluorescence lifetime and phosphorescence spectra were also discussed.     

Structural and magnetic properties of the Dy1−xThxFe3 system and some compounds of the form M0·1Th0·9Fe3

The structural and magnetic properties of the pseudobinary Dy_1?xTh_xFe₃ system, crystallizing in PuNi₃ type structure, have been investigated. For x<0·4 the magnetization vs temperature behavior can be understood on a ferrimagnetic coupling between the dysprosium and iron sublattices. For X=0·6 to 0·9 the magnetization vs temperature data show a marked transition at temperatures above 100°K. Lattice constants indicate a discontinuity in the lattice parameter c between X=0·6 and 0·5. Similar anomalies in the M vs T behavior were observed in M_0·1Th_0·9Fe₃ (where M=Sc, Y, Pr, Lu) compounds. These results can be explained on the basis of Friedel's model of transition metal d-bands.     

Radioactive decay of Os191 and Os191m

Beta and gamma spectra of Os¹⁹¹ were studied using a magnetic double-focusing beta-spectrometer and a scintillation spectrometer. The isomeric state Os^191m decays through the 74·4 ± 0·1 keV (E3/M4=50) transition with a half-lifeT _1/2=13·0 ± 0·5 hours. A continuous beta spectrum withE _max=147 ± 3 keV and the gamma transitions 41·83 ± 0·05 keV (E3), 82·5 ± 0·3 keV and 129·4 ± 0·1 keV (70%M1 + 30%E2) were observed in the decay of the ground state of Os¹⁹¹. The conversion coefficient of the last transition was determined as 1·94 ±± — 0·10. Gamma transitions with energies of 47 keV and 185·8 keV were not observed.     

Sonochemical synthesis and characterization of new nanostructures cobalt(II) metal-organic complexes derived from the azo-coupling reaction of 4-amino benzoic acid with anthranilic acid,salicylaldehyde and 2-naphtol

Nanostructures of three new cobalt(II) complexes, (CoL₁)·0.5DMF·1.5MeOH (1), [H₂L₁ = 5-(4-Carboxy phenyl azo) anthranilic acid], (Co(L₂)₂)·1.5MeOH (2), [HL₂ = 5-(4-Carboxy phenyl azo) salicylaldehyde] and (Co(L₃)₂)·0.5 DMF·0.5MeOH (3), [HL₃ = 1-(4-Carboxy phenyl azo) 2-naphtol], have been synthesized by the reaction of H₂L₁, HL₂ and HL₃ with Co(OAc)₂·4H₂O through sonochemical process. Calcination of the nano-sized compounds 1–3 yield Co₃O₄ nanoparticles at 450 °C under air atmosphere. These nanostructures were characterized by X-ray powder diffraction (XRD) and Scanning Electron Microscopy (SEM). Thermal stability of compounds 1–3 was studied by thermogravimetric (TG) and differential thermal analyses (DTA).     

Das Auger-Spektrum derL III- Schale von Wismut

A thin Bi layer is irradiated by X-rays so thatL-Auger electrons are emitted. A magnetic lens spectrometer is used to measure the electron spectrum. Energy, transition, and relativ intensity are given for 14 lines. Under the most favourable conditions the number ofL _III ionisations is about ten times that ofL _II ionisations. In this case only a small intensity ofL _II-Auger electrons is superposed on theL _III-Auger spectrum. The ratiod of intensities of line groupL _III M N to line groupL _III M M is found by extrapolation to bed=0·46±0·02. This combined with earlier results gives anL _III-Auger yielda ₃= 0·64±0·04. TheL _III fluorescenc yield isω ₃=0·36±0·04, correspondingly. A further application of the experimental method is described.     

Some nuclear and atomic properties of201Hg determined by conversion electron spectroscopy

Conversion electron measurements with an electrostatic spectrometer proved the existence of the 1,565±6 eV transition in²⁰¹Hg. The conversion intensity ratios,N ₁/N ₂ =1.2±0.2,N ₁/N ₃=1.1±0.2,N ₂/N ₃=0.92±0.15,N ₄/N ₃=0.03± 0.02 andN ₅/N ₃=0.04 ±0.02 were determined. These values agree with our calculations for the M1±E2 multipolarity with theE2/M1 mixing ratioδ ²=(l.l±0.3)xl0^?4 and exclude all pure multipolarities withL≦4. The total conversion coefficient for the aboveM1 +E2 mixture was evaluated to be (4.7±0.7)× 10⁴. The reducedB(M1, 1/2→3/2) probability was derived to be (3.9 ±1.2) × 10^?3 (e?/2Mc)². The natural widths of theN-subshell conversion lines in mercury were found to beΓ(N ₁)=8.3± 1.5,Γ(N ₂) =5.8±1.5 and Γ(N ₃) =6.5±1.0 eV. Monte Carlo calculations of electron scattering in matter yielded the conversion line shapes in qualitative agreement with the experiment.     

A study of the adsorption of oxygen on Ni(111) using auger electron spectroscopy: Chemical shifts and valence spectra

Auger electron spectra have been recorded when oxygen is adsorbed on a Ni(111) single crystal surface. For the coverage range θ < 1, an analysis of the plot of the peak to peak height (H) of the oxygen KVV (516 eV) transition versus the total number of molecules cm^2? impinging on the surface (molecular beam dosing) shows agreement with the kinetic mechanism proposed by Morgan and King [Surface Sci. 23 (1970) 259] for the adsorption of oxygen on polycrystalline nickel films. In this coverage range, no energy shifts of the nickel or oxygen Auger peaks were recorded.At coverages θ > 1 (standard dosing procedure) shifts in the valence spectra M_{2, 3}VV (61 eV) and L₃M_{2, 3}V (782 eV) of ?2.3 eV and ?1.8eV respectively are recorded at 1.4 × 10^?2 torr-sec. Up to these coverages no shift of the L₃VV transition (849 eV) is observed. A chemical shift of ?2.1 eV is recorded in the L₃M_{2, 3}M_{2, 3} Auger transition (716 eV) at 1.4 × 10^?2 torr-sec.In the coverage range θ > 1, shifts in the energy of the oxygen Auger peaks are observed. At 5.8 × 10^?3 torr-sec. the KVV (516 eV) and KL₁V (495.2 ± 0.3 eV) transitions show shifts of ?1.5 eV and ?(1.0 ±0.3) eV respectively. No shift up to this coverage is recorded in the KL₁L₁ (480.6 ± 0.3 eV) transition.     

High resolution Auger electron spectroscopy of metallic copper

Part of the LMM Auger spectrum from metallic copper has been studied in a high resolution X-ray photoelectron spectrometer. Fine structure not earlier reported has been observed. The main L₃M_4,5M_4,5 peak is very narrow, 1.0 eV, although the valence band is involved in the transition. The agreement between experimental and calculated Auger electron energies is very good. Since fine structure is found to be an intrinsic property in Auger spectra the interpretation of “satellite” peaks as due to electron—plasmon interactions should be used with care. The L₃M_4,5M_4,5 peak is very sensitive to the copper surface conditions. Surface oxygen affects the peak in a characteristic way.     

The low-energy electron spectrum from the EC-decay of 57Co: 0 eV up to 15 keV

The low-energy electron spectrum from the ⁵⁷Co decay has been examined in the region from 0 up to 15 keV at instrumental resolution ranging from 2 to 15 eV. Two electrostatic spectrometers and radioactive sources prepared by vacuum evaporation of ⁵⁷Co onto Al foils were utilized. Relative intensities of the main spectrum components have been obtained as follows: (TSE+LLX+Shake-off)/LMM/KLL/KLM/KMM/K−14.4/L−14.4/MN−14.4=116±12/51±4/59.7±1.8/15.2±0.4/1.15±0.07/49.6±1.5/5.05±0.15/0.79±0.02 where TSE means “true secondary electrons”. Absolute and relative energies of the LMM, KLL, KLM, and KMM Auger transitions in Fe have also been determined, as well as their relative intensities with the exception of the LMM lines, the shapes of which were strongly distorted due to the inelastic electron scattering and probably also chemical effects. From the measured conversion electron lines of the 14.4 keV M1 transition in ⁵⁷Fe, a transition energy of 14412.8±0.8 eV and the E2 admixture less than 8×10⁻⁶ were derived. Relative intensities of both the KL_2,3(M_4,5N₁) Auger line group and the M_4,5N₁−14.4 conversion line were found to be lower by about 30% for the “oxide” state of decaying ⁵⁷Co atoms than for the “metallic” state. Pronounced broadenings of narrow spectrum lines have been observed as a consequence of the oxidation of the ⁵⁷Co sources in the laboratory atmosphere. Natural widths for most of the KLL, KLM, and KMM Auger lines and those of the K, L₁, L₂, L₃, M₁, M₂, M₃ and N₁ atomic levels in ⁵⁷Fe were also determined.     

Many-electron effect in the Fe L3-M4,5M4,5 Auger electron spectrum of ultrathin Fe films grown on Cu(1 0 0)

D’Addato et al. [S. D’Addato, P. Luches, R. Gotter, L. Floreano, D. Cvetko, A. Morgante, A. Newton, D. Martin, P. Unsworth, P. Weightman, Surf. Rev. Lett. 9 (2002) 709] studied the variation with Fe coverages in the relative Fe L₃-M_4,5M_4,5 Auger electron spectroscopy (AES) spectral satellite intensity of ultrathin Fe films grown on Cu(1 0 0) by sweeping photon excitation energy through the Fe L₂-level ionization threshold. They interpreted that the M_4,5 hole in the L₃M_4,5 double-hole state created by the L₂-L₃M_4,5 Coster–Kronig (CK) decay remains localized for longer than the L₃-hole lifetime for the 0.3 and 10 ML coverages but has a lifetime comparable to the L₃-hole lifetime for the 1 ML coverages. The present many-body theory shows that when the M_4,5 hole created either by the CK decay or by the L₃M_4,5 shakeoff hops away from the ionized atomic site and becomes completely screened out prior to the L₃-hole decay, the Fe L₂-L₃M_4,5-L₃-M_4,5M_4,5 AES main line as well as the Fe L₃ M_4,5 (satellite)-L₃-M_4,5M_4,5 one, both of which are identical in line shape to the Fe L₃-M_4,5M_4,5 one, dominate in the Fe CK preceded AES spectrum. The present analysis shows that the delocalization time of the M_4,5 hole created in the 1 ML Fe/Cu(1 0 0) system by the L₂-L₃M_4,5 CK decay is much shorter than the L₃-hole lifetime so that the Fe L₃-M_4,5M_4,5 AES spectral line shape hardly changes, except for the presence of a very weak spectator L₂-L₃M_4,5-M_4,5M_4,5M_4,5 AES satellite, when the photon excitation energy is swept through the Fe L₂-level ionization threshold. For the 0.3 ML coverages the M_4,5-hole delocalization time is still shorter than the L₃-hole lifetime.     

An experimental investigation of the onset of theL 2-L 3 M 4 andL 2-L 3 M 5 Coster-Kronig transitions forZ>90

L-M coincidence measurements were made on x rays from the radioactive decays of ₉₆ ²⁴⁴ Cm, ₉₄ ²³⁸ Pu, and ₉₂ ²³² U. The observation ofM x rays in coincidence with theL ₃ N _{4, 5} transition indicates that the onset of theL ₂-L ₃ M ₅ Coster-Kronig transition takes place atZ=91 or 92. The measured ratio of theM x-ray counting rates, coincident with theL ₃ N _{4, 5} andL ₂ M ₄ transitions, establishes that both theL ₂-L ₃ M ₄ and theL ₂-L ₃ M ₅ transitions are energetically possible forZ≧94, but the results do not rule out the possibility that these transitions begin as low asZ=92. The measurement ofL-M x-ray coincidences, together with relative Coster-Kronig electron intensities from theory or experiment, provides a new way to measure the totalL ₂-L ₃ Coster-Kronig transition probability,f ₂₃, at highZ for radioactive sources where the primary vacancies are created primarily in theL ₂ andL ₃ subshells. The present result atZ=94 indicates that the theoretical calculations of McGuire of the relative partial Coster-Kronig transition rates forL ₂-L ₃ M _4,5 are accurate to within 10 percent.     

Experimental and theoretical insight into the cooperativity effect in composite wax powder and ternary complex of coronene with CH4 and Mn+ (Mn+ = Li+, Na+, K+, Be2+, Mg2+ or Ca2+)

The experimental infrared (IR) spectrum of composite wax powder was investigated. The frequency shifts of the C=C anti-symmetrical stretching mode were observed and the experimental cooperativity effect involving Na⁺···π interaction was suggested. In order to further reveal the nature of cooperativity effect, the interaction energies in Mⁿ⁺···coronene···CH₄ (Mⁿ⁺ = Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺ or Ca²⁺) as the model systems of composite wax powder were calculated by using the B3LYP, M06-2X and MP2 methods with 6-311++G^** basis set. The results show that the Mⁿ⁺···π interactions were strengthened upon the formation of ternary complexes. Although the changes of absolute values of the interactions between CH₄ and coronene were not obvious, the relative values were considerably significant upon the formation of ternary complexes. The cooperativity effect was perhaps the reason for the formation of notable advantage of composite wax powder upon the introduction of surfactant with cation into wax powder. Reduced density gradient and atoms-in-molecules analysis confirm the cooperativity effect in Mⁿ⁺···coronene···CH₄, and reveal the nature of the formation of the predominant advantage of composite wax powder.     

Raman spectroscopic study of the hydrogen and arsenate bonding environment in isostructural synthetic arsenates of the variscite group—M3+ AsO4·2H2O (M3+ = Fe,Al, In and Ga): implications for arsenic release in water

The Raman spectra of synthetic compounds equivalent to the variscite group: FeAsO₄·2H₂O AlAsO₄·2H₂O, GaAsO₄·2H₂O, and InAsO₄·2H₂O are reported. In particular, upon comparison of FeAsO₄·2H₂O to AlAsO₄·2H₂O, it is observed that the Type II (weak) H‐bond lengths in the latter are slightly longer, which is postulated to affect the stability (As release) in water at pH 5 and 7. Arsenate stretching and bending vibrations were found to be distinct in terms of spectral structure and therefore well suited for fingerprinting. The calculated As O bond strengths from existing crystallographic data showed no significant variations. The strongest ν₁ (AsO₄³⁻) stretch was used to monitor the As O bonding interactions in the four As O M units, where a shift of 114 cm⁻¹ was observed in the order FeAsO₄·2H₂O (lowest) < InAsO₄·2H₂O < GaAsO₄·2H₂O < AlAsO₄·2H₂O (highest); this order also followed exactly the measured arsenic release of these phases. This shift in ν₁ (AsO₄³⁻) position was rationalized to stem from the differences in the electronegativities of the M³⁺ cations. The trends mentioned above were verified and found to also hold for the isostructural phosphate analogues strengite (FePO₄·2H₂O) and variscite (AlPO₄·2H₂O) using published data. Therefore, it is postulated that, as observed with the stability of solution complexes, there may be a correlation between the electronegativity of the M³⁺ cation in these isostructural phases and their stability (As or P release) in water. Copyright © 2010 John Wiley & Sons, Ltd.     

Influence of the surface on the quantum P.E.M. effect in InP

The photoelectromagnetic effect of InP is studied in quantizing magnetic fields at 4·2 K in an energy range 1·4–1·5 eV for linearly polarized light. Depending on the sample surface condition two types of spectral oscillations may appear, those associated with interband transitions between Landau levels or the LO phonon type usually seen in photoconductivity. An analysis of the spectral oscillations gives: E₀ = 1·423±0·001 eV; Δ₀ = 0·102±0·006 eV; hω_L = 0·036 eV.     

High order electron paramagnetic resonance transitions of Gd3+ in Pr2Zn3(NO3)12·24H2O single crystals

Electron paramagnetic resonance of Gd³⁺ in Pr₂Zn₃(NO₃)₁₂ · 24H₂O single crystals has been studied at ∼ 9.45 GHz and at 285 K. In addition to the allowed fine structure lines (ΔM=± 1) some weak low field lines identified as ΔM = ± 2 transitions have been observed.     

Luminescence and absorption of Tb3+in mo·Al2O3·B2O3·Tb2O3 glasses

Quantum yields of the green Tb luminescence for 254 nm excitation of glass compositions in the system MO·Al₂O₃· B₂O₃·Tb₂O₃ (M = Mg, Ca, Sr, Ba and Zn) were studied in relation to absorption and excitation spectra. Yields as high as 80% were observed. The Tb 4f-5d absorption maximum ranges from 218 to 232 nm, always at a longer wavelength than the glass matrix absorption. The yield strongly depends on the spectral position of the 4f-5d absorption, due to competing impurity absorption at 254 nm.