The investigations on K and L X-ray fluorescence parameters of gold compounds

The study aimed to determine the chemical effects on the K and L X-ray intensity ratios and the K and L X-ray production cross sections for gold compounds. The K shell fluorescence yields and L shell average yields were also investigated. The samples were excited by 59.5 keV γ-rays from an ²⁴¹Am annular radioactive source and 123.6 keV γ-rays from a ⁵⁷Co annular radioactive source. K and L X-rays emitted from samples were counted by an Ultra-LEGe detector with a resolution of 0.150 keV at 5.9 keV. The experimental values were compared with theoretical, the semi-empirical and other experimental values.     

K-shell ionization of low Z elements in ion–solid collisions and applicability of local plasma approximation

K-shell vacancy production cross sections are measured using X-ray technique, in collisions of highly charged fluorine ions with various solid targets such as, Cl, K, Fe and Cu, at energies from 50 to 110 MeV. The experimental data is compared with an ab initio model based on local plasma approximation (LPA) and the usually employed ECPSSR. A detailed comparison with the LPA model is presented as a function of generalized perturbation strength.     

Lι, Lα, Lβ and Lγ X-ray fluorescence cross-sections of heavy elements for the exciting photons energy 38.18, 43.95, 50.21 and 59.5 keV

The cross-sections for the production of L_ι, L_α, L_β and L_γ X-ray fluorescence (XRF) in Er, Ta, W, Au, Hg, Tl, Pb and Bi by photons with energies in the range 38–59.5 keV have been measured, using a standard doublereflection experimental set-up. Measurements have been performed using an annular 241 Am primary source and X-ray emitting secondary-exciter system. Experimental cross-sections have been compared with the theoretically calculated values of L X-ray cross-sections and fairly good agreement is observed between the experimental and theoretical values.     

Calculation of vacancy transfer probabilities from K to L shell using the X-ray fluorescence parameters

The probabilities for vacancy transfer from the K to the L shell (η_KL), have been calculated for eleven high atomic number elements using the measured K and L shells X-ray production cross-sections. The targets were excited by 123.6 keV photon from a ⁵⁷Co annular radioactive source. K and L X-rays emitted by samples were counted with a Si(Li) detector. The measured values of η_KL were compared with the theoretical values and our early papers.     

K shell,L shell–subshell and M shell–subshell photoeffect cross-sections in elements between Tb (Z=65) and U (Z=92) at 123.6 keV

In this paper, we report on measurements of K shell, L shell–subshell and M shell–subshell photoeffect cross-sections for 21 high-atomic-number elements between Tb (Z=65) and U (Z=92) at 123.6 keV. These photoeffect cross-sections have been measured by using our earlier measurements of the K-shell X-ray production cross-sections. The measured photoeffect cross-sections have been compared with calculated theoretical values. It is clear that the results compare well with theoretical values within an experimental average error. At 123.6 keV, these cross-sections have been measured for the first time. The results have been plotted versus atomic number.     

Measurement of L subshell photoionisation cross sections of Th and U at 22.6, 25.8, 29.2 and 32.9 kev

Bremsstrahlung from an X-ray tube was used to excite secondary targets of Ag, Sn, I and Ba to get nearly monochromatic excitation energies of 22.6, 25.8, 29.2 and 32.9 keV, respectively. Th and U were used as targets. The L X-ray fluorescence cross sections of different lines from the targets have been measured. Of the several methods to obtain L subshell photoionisation cross sections from these fluorescence data, the merits and demerits of four common methods have been explained and the method with least uncertainty was suggested as the best one for such analysis. Following this method, with intensities of the resolved L_γ lines, three L subshell photoionisation cross sections have been obtained using six different sets of atomic parameters. The variation of these cross sections with different atomic parameters has been discussed. For σ₁, all the derived values are within 30% of one other while for σ₂ and σ₃, they are within 12%. Measured cross sections have been compared with the data of others and with the theoretical values of Scofield. Finally, the intensity ratios of different L lines have also been compared with available data and the theoretical values. Within experimental errors, our data are in good agreement with the data of others and with the theoretical predictions.     

Characterisation of salt films on dissolving metal surfaces in artificial corrosion pits via in situ synchrotron X-ray diffraction

The salt films formed on metal surfaces dissolving inside artificial corrosion pits formed in 1 M HCl have been probed with synchrotron X-ray diffraction. NiCl₂ · 6H₂O is the main phase in the salt film on nickel, whereas salt films on both iron and 316 L stainless steel are predominantly FeCl₂ · 4H₂O. However, the salt film on iron has a very fine homogeneous crystallite size whereas that on stainless steel is much coarser. The potential-dependence of the film formed on iron has been determined.     

Signal enhancement in solution-cathode glow discharge — optical emission spectrometry via low molecular weight organic compounds

HCOOH, CH₃COOH, and CH₃CH₂OH were used as chemical modifiers in a solution-cathode glow discharge. Emission was measured directly from the discharge, without a gas–liquid separator or a secondary excitation source. Emission from Ag, Se, Pb, and Hg was strongly enhanced, and the detection limits (DL) for these elements were improved by up to an order of magnitude using a combination of HCOOH and HNO₃ compared to using HNO₃ alone. The DL was measured for Mg (1 μg/L), Fe (10 μg/L), Ni (6 μg/L), Cu (6 μg/L), Pb (1 μg/L), Ag (0.1 μg/L), Se (300 μg/L), and Hg (2 μg/L). Coefficients of determination (R²) were between 0.9986 and 0.9999. A voltage of 1 kV was used, which produced a current of approximately 70 mA.     

K-edge angiography utilizing a tungsten plasma X-ray generator in conjunction with gadolinium-based contrast media

The tungsten plasma flash X-ray generator is useful in order to perform high-speed enhanced K-edge angiography using cone beams because K-series characteristic X-rays from the tungsten target are absorbed effectively by gadolinium-based contrast media. In the flash X-ray generator, a 150 nF condenser is charged up to 80 kV by a power supply, and flash X-rays are produced by the discharging. The X-ray tube is a demountable diode, and the turbomolecular pump evacuates air from the tube with a pressure of approximately 1 mPa. Since the electric circuit of the high-voltage pulse generator employs a cable transmission line, the high-voltage pulse generator produces twice the potential of the condenser charging voltage. At a charging voltage of 80 kV, the estimated maximum tube voltage and current were approximately 160 kV and 40 kA, respectively. When the charging voltage was increased, the characteristic X-ray intensities of tungsten K_α lines increased. The K_α lines were clean, and hardly any bremsstrahlung rays were detected. The X-ray pulse widths were approximately 110 ns, and the time-integrated X-ray intensity had a value of approximately 0.35 mGy at 1.0 m from the X-ray source with a charging voltage of 80 kV. Angiography was performed using a film-less computed radiography (CR) system and gadolinium-based contrast media. In angiography of non-living animals, we observed fine blood vessels of approximately 100 μm with high contrasts.     

Infrared spectroscopic study of the protonated ligand salts of a 15-membered dioxa-diaza macrocycle

The 15-membered mixed dioxa-diaza macrocycle 5,6,14,15-dibenzo-1,4-dioxa-8,12-diazacyclopentadeca-5,14-diene (L) by reactions with a series of sodium salts NaX (X = picrate, ClO₄, BF₄, PF₆ and BPh₄) in acetonitrile and methanol solution yielded the protonated macrocyclic salts with different proton-to-ligand ratio as well as different modes of inside and outside macrocycle protonation and hydrogen bonding systems. Infrared spectra of the ion-pair compounds [H(L)]X with intraligand protonation as well as [H(L)₂]X and [H₂(L)₃](X)₂ with interligand protonation, have been studied. The results obtained are discussed with respect to reported X-ray structure data of these compounds.     

Oscillator strength measurements of the 5s5p 3P1 → 5snd 3D2 Rydberg transitions of cadmium

We report oscillator strengths distribution in the bound region of cadmium corresponding to the 5s5p ³P₁ → 5snd ³D₂ (21 ≤ n ≤ 52) Rydberg transitions. The experiment was performed using two frequency doubled dye lasers simultaneously pumped by a common Nd:YAG laser in conjunction with an atomic beam set-up. The absolute photoionization cross section of the 5s5p ³P₁ intermediate state at the 5s ²S_1/2 ionization threshold has been measured as 20 (4) Mb using the saturation technique. The measured value of the photoionization cross section at threshold is used to extract the f-values of the above mentioned Rydberg transitions.     

Separated projectile and targetK x-ray production in symmetric heavy ion collisions as a function of the target thickness

Cross sections for projectile and targetK x-ray emission have been measured as a function of the target thickness for the symmetric systems Ni-Ni, Cu-Cu, Nb-Nb, Ag-Ag at energies between 75 and 105 MeV. The projectileK x-rays were separated from the target ones by using the Doppler shift. K_α and K_β energy shifts and K_β to K_α intensity ratios were also determined and used to calculateM- andL-ionization and the correspondingK-fluorescence yield for both collision partners. At non vanishing small target thicknesses, the targetK-vacancy production cross section is generally larger than that of the projectile. By analysing the target thickness dependence of the cross sections with a two component model which takes also into account the evolution of the projectileM-,L- andK-shell population inside the solid, targetK-vacancy sharing and cross sections forKK electron capture in symmetric systems could be determined. These results are in good agreement with molecular orbital model predictions.     

Synthesis,crystal, molecular and electronic structures of thiocyanate ruthenium complexes with pyridine and its derivatives as ligands

The complexes [Ru(SCN)₂(PPh₃)₂(L)₂], where L = py and γ-pic, and [Ru(SCN)₂(PPh₃)₂(L)], where L = py-2-CH₂NH₂ and py-2-CH₂O, have been prepared and studied by IR, NMR, EPR, UV–Vis spectroscopy and X-ray crystallography. The complexes were prepared in the reactions of [RuCl₂(PPh₃)₃] with pyridine, γ-picoline, 2-(aminomethyl)pyridine and 2-(hydroxymethyl)pyridine in methanol solutions. The electronic structures of the obtained compounds have been calculated using the DFT/TD-DFT method.     

Geometric shielding corrections for calculation of electron scattering by CO2, C2H2, CHCl3, CH2Cl2, CH3Cl,CHF3, CH2F2 and CH3F at 30–5000 eV

Taking into account the changes of the geometric shielding effect in a molecule as the incident electron energy varies, an empirical fraction, which depends on the energy of the incident electrons, the target's molecular dimension and the atomic and electronic numbers in the molecule, is presented. Using this empirical fraction, a new formulation of the additivity rule is proposed. Using the new additivity rule, the total cross sections of electron scattering by CO₂, C₂H₂, CHCl₃, CH₂Cl₂, CH₃Cl, CHF₃, CH₂F₂ and CH₃F are calculated at the Hartree–Fork level at 30–5000 eV. The quantitative total cross sections are compared with those obtained by experiments and other theories, and good agreement is obtained over a wide energy range, especially above 100 eV.     

Synthesis,characterization and antibacterial activity of some new triphenyltin(IV) sulfanylcarboxylates: Crystal structure of [(SnPh3)2(p-mpspa)], [(SnPh3)2(cpa)] and [(SnPh3)2(tspa)(DMSO)]

Five new triphenyltin(IV) sulfanylcarboxylates of the general formula [(SnPh₃)₂L] (L = pspa, tspa, fspa, p-mpspa or cpa, where p = 3-(2-phenyl)-, t = 3-(2-thienyl)-, f = 3-(2-furyl)-, p-mp = 3-(4-methoxyphenyl)-, spa = 2-sulfanylpropenoato and cpa = 2-cyclopentilyden-2-sulfanylacetate) have been synthesized by reacting triphenyltin(IV) hydroxide with the corresponding acid in ethanol/acetone. The complexes have been characterized by elemental analysis and mass spectrometry and by vibrational and NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopies. In the case of [(SnPh₃)₂(p-mpspa)] and [(SnPh₃)₂(cpa)], X-ray structural studies showed that in both compounds each Sn atom is coordinated to three phenyl C atoms and to one S or O atom of the bridge ligand L. All five complexes are active against strains of Staphylococcus aureus, but are inactive against Escherichia coli and Pseudomonas aeruginosa. From a solution of [(SnPh₃)₂(tspa)] in DMSO-d₆ the new complex [(SnPh₃)₂(tspa)(DMSO)] was isolated. The single-crystal X-ray diffractometric study of this complex is also reported, showing that both Sn atoms are bridged by the tspa ligand, whereas the molecule of DMSO is coordinated to one of the tin atoms via the oxygen atom.     

Synthesis,spectroscopic, magnetic and thermal properties of bimetallic salts, [Ni(L)][MCl4] {where M = Co(II), Zn(II), Hg(II) and L = 3,7-bis(2-aminoethyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane}. X-ray structure of [Ni(L)][CoCl4]

New bimetallic complex salts corresponding to the formulation [Ni(L)][MCl₄] have been synthesized by the facile reaction between [Ni(L)](ClO₄)₂ and [MCl₂(PPh₃)₂] in high yields {where M = Co(II), Zn(II), Hg(II) and L = 3,7-bis(2-aminoethyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane}. The complexes were characterized by IR, electronic spectra, TGA/DSC, magnetic moment and conductivity measurements. The X-ray crystal structure for [Ni(L)][CoCl₄] clearly establishes the cationic–anionic interaction. It crystallizes in the space group P1 with unit cell dimensions a = 7.1740(15) Å, b = 8.1583(16) Å and c = 8.3102(16) Å. A square-planar geometry is evident for the [Ni(L)]²⁺ cation while the anion is found to be tetrahedral. A two-step thermolytic pattern is observed in the pyrolysis of the bimetallic complex salts.     

Determination of mass attenuation coefficients,effective atomic and electron numbers for some natural minerals

The total mass attenuation coefficients (μ_m) for SiO₂ {Quartz (1 1 0 1), Quartz (1 1 0 0) and Quartz (0 0 0 1)}, KAlSi₃O₈ {Orthoclase (0 1 0), Orthoclase (1 0 0)}, CaSO₄·2H₂O (gypsum), FeS₂ (pyrite) and Mg₂Si₂O₆ (pyroxene) natural minerals were measured at 22.1, 25.0, 59.5 and 88.0 keV photon energies. The γ- and X-rays were counted by a Si(Li) detector with a resolution of 160 eV at 5.9 keV. Atomic and electronic cross sections (σ_t and σ_e), the effective atomic and electron numbers or electron densities (Z_eff and N_eff) were determined using the obtained μ_m values for investigated samples.     

Magneto-structural correlation and low temperature heat capacity of a Mn (III) quadridentate Schiff-base coordination compound

A new Mn (III) Schiff-base coordination compound, [Mn(L)(NCS)]₂ (H₂L = N,N′-bis(5-chlorosalicylidene)-1,2-diaminoethane), has been synthesized and characterized structurally and magnetically. The target compound is a phenoxo-bridged dimeric compound with the isothiocyanate coordinating in a usual bent mode. A magnetic susceptibility study reveals that the target compound exhibits antiferromagnetic intra-dimer coupling between Mn (III) ions. The low temperature heat capacity of the compound over the temperature range (2 to 300) K has been measured using the heat capacity option of a Quantum Design Physical Property Measurement System (PPMS). The thermodynamic functions in the experimental temperature range have been determined by curve fitting. The standard entropy and enthalpy of the as-prepared compound at T = 298.15 K have been calculated to be (924.52 ± 10.17) J · K⁻¹ · mol⁻¹ and (133.47 ± 1.47) kJ · mol⁻¹, respectively.     

Jahn–Teller phase transition in Cu0.50TiO(PO4): Powder structural characterization of the β-variety and thermal study

The thermal study of Cu_0.50TiO(PO₄), by X-ray diffraction and DSC, shows a phase transition α → β with a hysteresis (∼600 °C during heating; ∼300 °C during cooling). Single crystals have been obtained for the α-phase but the β-phase can only be stabilised at room temperature as a powder mixture with α. Structural characterization of the β-variety has been done with diffraction data (X-ray Cu Kα₁ and neutrons) using a powder rich in β-phase (α(20%) + β(80%)). A monoclinic cell (a = 7.1134(7) Å; b = 7.7282(7) Å; c = 7.3028(7) Å; β=119.30(1)°; V = 350.1(1) Å³) has been found for β-phase, space group P2₁/c. An “ab initio” structure determination has been done, and the Rietveld refinement leads to cR_wp = 0.150 and R_B = 0.041. The results from the X-ray data were confirmed by refinements from neutron data.Similarly to the α-phase, the structure of β-Cu_0.50TiO(PO₄) can be described as a TiOPO₄ framework constituted of chains of tilted corner-sharing [TiO₆] octahedra running parallel to the c axis and cross linked by [PO₄] tetrahedra. Ti atoms are displaced from the centres of the octahedral units, leading to long (2.27 Å) and short (1.73 Å) Ti–O(1) bonds. The [CuO₆] octahedra exhibit a typical Jahn–Teller distorted coordination with four short equatorial Cu–O bonds (2 × 1.93 Å and 2 × 2.06 Å), and two longer apical Cu–O bonds (2 × 2.33 Å). The two longer Cu–O bonds are almost parallel to the b axis.The transition from the α to the β-phase is characterized by a “rocking” of the Jahn–Teller elongation from the (a,c) plane to the b direction accompanied by a relatively strong expansion of the cell volume.