Experimental L x‐ray fluorescence cross‐sections for elements with 45 ≤ Z ≤ 50 at 7 keV by synchrotron radiation photoionization

L x‐ray fluorescence cross‐sections for elements with 45 ≤ Z ≤ 50 were measured at 7 keV using synchrotron radiation photoionization. The experimental set‐up provided a linearly polarized monoenergetic photon beam producing a low background and improving the signal‐to‐noise ratio. The data obtained for the L lines, Ll, Lα, Lβ_I, Lβ_II, Lγ_I and Lγ_II, were grouped considering the transition scheme, the energies of the emission lines and the detector resolution. Results for the experimental cross‐sections obtained were compared with theoretical values using two different data tables. In general, it was found that the experimental fluorescence cross‐sections are slightly higher (7–10%) than the theoretically calculated data and in some cases these differences are up to 40%. Copyright © 2005 John Wiley & Sons, Ltd.     

Measurements of Coster–Kronig enhancement factors of some elements in the atomic number range 66 ≤ Z ≤ 72

The Lι, Lα, Lβ and Lγ x‐ray production cross‐sections in four elements with Z ranging from 66 to 72 at seven different energies in the interval 8.265–11.730 keV were measured. Experimental measurements were carried out on a few elemental samples to examine the effect of Coster–Kronig transitions on fluorescence cross‐sections for the L x‐ray line using an Si(Li) detector system with an energy resolution of 160 eV at 5.96 keV x‐ray energy. Absolute values of L x‐ray cross‐sections were calculated with incorporation of the enhancement due to the Coster–Kronig effect for these elements. The measured enhancement factors are smaller than predicted by theory. Copyright © 2003 John Wiley & Sons, Ltd.     

L x‐ray fluorescence cross‐sections of heavy elements in the atomic region 57 ≤ Z ≤ 71 excited by 17.78 keV photons

L x‐ray fluorescence cross‐sections (σ_Lα, σ_Lβ, and σ_Lγ) were measured with an accuracy of 6% (except for the Lγ x‐ray line around 8%) for La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb and Lu at an excitation energy of 17.78 keV. Relative intensities I_Kβ/I_Kα and I_Lγ/I_Lα were also measured for the same elements. The measured cross‐sections were compared with experimental and theoretical values. Measurements of the emitted x‐rays were performed using an Si(Li) detector. Copyright © 2004 John Wiley & Sons, Ltd.     

Characterization of the Metrology beamline at the SOLEIL synchrotron and application to the determination of mass attenuation coefficients of Ag and Sn in the range 3.5 ≤ E ≤ 28 keV

This work presents the new Metrology beamline at the SOLEIL synchrotron facility and a first attempt to quantitative measurements of mass attenuation coefficients for Ag and Sn performed on the hard X‐ray branch. We first describe the beamline itself and the characterization performed of the unfocused monochromatic beam running mode. We performed a first experimental measurement of mass attenuation coefficients in the range 3.5 ≤ E ≤ 28 keV and we also derived the K‐absorption and L‐absorption jump ratios. The results are compared with theoretical values as well as with other experimental data and agree well with previous published values. Copyright © 2011 John Wiley & Sons, Ltd.     

Elastic scattering cross section of photons by water: limits for the free atom approximation

Several papers can be found in the literature in which elastic and inelastic experimental scattering cross sections of photons by water with energies in the keV range are measured. Usually, the authors use some kind of normalization with theoretical values, because of the difficulties in obtaining some parameters necessary to obtain absolute cross sections from the measurements. A reasonable range of momentum transfer has been covered, but nevertheless, inconsistencies and gaps still remain. In this work, we address the problem performing absolute cross section measurements in the high momentum transfer region (0.33 Å^?1 ≤ x ≤ 4.5 Å^?1), where no structure effects can be observed. We compare the results with theory to validate it in an intermediary region (0.33 Å^?1 ≤ x ≤ 1.72 Å^?1) and then use the experimental values to normalize data in the low‐energy region (0.078 Å^?1 ≤ x ≤ 1.72 Å^?1) to obtain the experimental cross section in that region. From the comparison, we concluded that for momentum transfers, x between 0.7 and 4.5 Å^?1 the scattering can be considered as being due to free atoms in free molecules. Therefore, the scattering cross sections may be considered as a sum of those from free atoms. Theoretically, the scattering cross sections can be obtained from the form factors as well as from the second‐order perturbation theory (S‐matrix) because there is no significant difference between both. On the other hand, for x ≤ 0.7 Å^?1, interference between the photon‐scattered amplitudes due to liquid structure generates oscillations in the cross section values. Copyright © 2014 John Wiley & Sons, Ltd.     

2p3/2−13x−1–3x−13d3/2−1 x‐ray satellites in the Lα2 region

The energies and intensities of the various transitions corresponding to the transition scheme 2p_3/2^?13x^?1–3x^?13d_3/2^?1 (i.e. L₃M_x–M_xM₄) were used to compute theoretical Lα₂ satellite spectra in 13 elements in the atomic number range of 62 ≤ Z ≤ 90. The energies were calculated using available HFS data on K–LM and L–MM transition energies. The intensities of all the possible transitions were estimated by considering cross‐sections for the Auger transitions simultaneous to a hole creation and then distributing statistically the total cross‐sections for initial two‐hole states 2p_3/2^?13x^?1 (L₃M_x) amongst various allowed transitions from these initial states to 3x^?13d_3/2^?1 (M_xM₄) final states. Each transition was assumed to give rise to a Gaussian line and the overall spectrum was computed as the sum of these Gaussian curves. The calculated spectra were compared with the available measured Lα satellite spectra. The peaks in the theoretical satellite spectra were identified as the experimentally reported satellites Lα_s, La₁₃, La₁₄ and La₁₇, which lie on the high‐energy side of the Lα₂ dipole line. Copyright © 2005 John Wiley & Sons, Ltd.     

Measurements of L subshell and L shell x‐ray fluorescence cross‐sections for U and Th

The Ll, Lα_{1, 2}, Lη, Lβ₆, Lβ_{2, 4, 15, 17}, Lβ_{1, 3, 5}, Lβ_{9, 10}, Lγ₁, Lγ_{2, 3, 6, 8}, Lγ_4,4′ and Lγ₅ x‐ray fluorescence cross‐sections for U and Th were measured at 59.5 keV incident photon energy by using theoretical L_i subshell photoelectric cross‐sections, fluorescence and Coster–Kronig yields and fractional emission rates, and calculated theoretically by using atomic parameters. The measured values were compared with the theoretical values and experimental results available in the literature. Copyright © 2003 John Wiley & Sons, Ltd.     

Synchrotron radiation induced X‐ray production cross sections of 66Dy at energies across its Li (i = 1–3) subshell absorption edges

The X‐ray production (XRP) cross sections for the ₆₆Dy L_k (k = l, α, η, β_2,6,7,15, β_1,6, β_1,3,4,6, β_2,7,15, γ_1,5, γ₂,₃) emission lines have been measured by tuning the incident synchrotron radiation at energies over the range 7.8–9.2 keV and ~10–370 eV above the respective L_i (i = 1–3) absorption edges. These measurements aim to check the reliability of the independent particle approximation models used to generate the theoretical data sets of different physical parameters required to calculate the XRP cross sections and also investigate the influence of many body effects on the photoionization process. The measured values have been compared with 4 sets of XRP cross sections calculated using the Dirac–Fock model‐based X‐ray emission rates, 2 sets of the L_i (i = 1–3) subshell photoionization cross sections deduced from the self‐consistent Dirac–Hartree–Fock model‐based values and the nonrelativistic Hartree–Fock–Slater model‐based values, and 2 sets of the fluorescence (ω_i) and Coster–Kronig (f_ij) yields. The present measured Lγ_2,3 (originating from decay of the L₁ subshell vacancies) XRP cross sections are found to be significantly higher than different sets of theoretical values, whereas a good agreement is generally observed for the various other XRP cross sections and relative intensities.     

Cascade Mi (i = 1–5) subshell X‐ray emission at incident photon energies across the Lj (j = 1–3) subshell absorption edges of 66Dy

The total M shell and the M_k (k = ξ, αβ, γ, m) X‐ray production cross sections for ₆₆Dy have been measured at incident photon energies across its L_j (j = 1–3) subshell absorption edge energies, ranging 7.8–9.2 keV. This study aims to investigate the evolution of the probability for cascade decay of L_j subshell vacancies as the tunable incident energy ionizes progressively different ₆₆Dy L_j subshells. The experimental X‐ray production cross sections have been compared with theoretical ones calculated using the nonrelativistic Hartree–Fock–Slater (HFS) model‐based photoionization cross sections; three sets of the X‐ray emission rates, fluorescence and Coster–Kronig yield based on the nonrelativistic Hartree–Slater (NRHS) model, Dirac–Hartree–Slater (DHS) model and Dirac–Fock (DF) model; the L_j (j = 1–3) subshell to the M_i (i = 1–5) subshell vacancy transfer probabilities evaluated in the present work. Presently measured total M shell and the M_αβ X‐ray production cross sections are found to be significantly lower than the theoretical ones evaluated using physical parameters based on the relativistic Dirac–Fock/Dirac–Hartree–Slater model calculations, whereas a much better agreement is observed with respect to the NRHS model‐based calculations; however, the measured X‐ray production cross sections are still systematically lower than the NRHS values.     

Inner-shell ionization by relativistic electron impact

K-, L andM-shell ionization cross sections have been measured for 23 elements, 12≦Z≦92, after bombardment with relativistic electrons, 15≦E ₀65MeV, by means of high resolution semiconductor detectors and a recently developed gas-scintillation proportional counter. For constant electron bombarding energyE ₀ the ionization cross sections follow a power law dependence,σ∽Z ^?α, and forE ₀=50MeV we deducedα =2.45±0.02 for theK shell andα=3.00 ±0.09 for theL shell. The observedZ dependence exhibits significant systematic deviations from theoretical predictions which exceed the experimental values up to 15 % at lowZ elements for theK shell and on the average about 11% for theL andM shell. The same behaviour of too low experimental values, i.e. an overestimation by the theory, is observed for the energy dependence of the cross sections for all shells. A scaling behaviour describing theZ andE ₀ dependence for allK-, L andM-shell data points is observed which also predicts the experimental values by other groups at lower and higher energies correctly. The comparsion of the measuredLΒ/Lα, andLγ/Lα intensity ratios for highZ elements with the values obtained by other groups in the energy range 0.3≦E₀≦1,000 MeV exhibits an increase with bombarding energy that cannot merely be explained by the energy dependence of the subshellionization cross sections for theL shell. An attempt to explain this effect with the change of the Coster-Kronig transition probability is described.     

MREI‐model calculations of Raman‐active modes in layered mixed crystals TiS2−xSex(0≤x≤2)

A modified random‐element isodisplacement model has been developed and used to calculate the concentration dependence of the wavenumbers of Raman‐active modes in mixed crystal system, TiS_2−xSe_x(0≤x≤2). Earlier theoretical work, based on the Jaswal model, predicted a phase transition in this system on cooling up to 125 K temperature for the composition x ≥ 1.2. But recently reported resistivity measurements did not find the existence of any phase transition for a composition x < 1.4 on cooling. Our calculations show these findings and give remarkably better fitting to Raman data. The estimated values of the force constants are found to lie generally in the range 10⁵–10⁶ amu cm⁻². Copyright © 2007 John Wiley & Sons, Ltd.     

Experimental and theoretical studies on the one‐photon and two‐photon properties of a series of carbazole derivatives containing styrene

Symmetric‐type carbazole derivatives show great potential for application in two‐photon absorption (TPA) materials and organic light‐emitting diodes. The absorption spectra and fluorescence emission spectra of three different N‐alkyl symmetric‐type carbazole derivatives were investigated. The density functional theory (DFT) time‐dependent‐DFT//Becke, three‐parameter, Lee–Yang–Parr/6‐31 G* method has been used to theoretically study one‐photon absorption properties. The computational results are in good agreement with the available experimental values. The two‐photon excited fluorescence of the compounds was surveyed by 120 fs pulse at 790 nm Ti: sapphire laser operating at 1 kHz repetition rate. Two‐photon excited fluorescence was obtained in the range of 380–600 nm, and TPA cross‐sections were calculated. The TPA properties of the series of compounds were investigated by the ZINDO/single and double electronic excitation configuration interaction method. The influence of the chemical structure of the compounds on two‐photon optical properties was discussed. The results show how the different changes in one‐photon absorption and TPA properties on the basis of lengthening the conjugated bridge and the different carbazole N‐alkyl substituents are attributed to the transition dipole moment in the excited process. Copyright © 2011 John Wiley & Sons, Ltd.     

Energy dependence of photon-inducedL shell x-ray intensity ratios in Ta and W

TheL shell x-ray intensity ratios have been measured for the elements Ta and W by photoionization ofL shell electrons in the photon energy region 14⩽E⩽44 keV. The experimental results are compared with those calculated at the photon energies used in the present measurements. The measured values show fairly good agreement with the calculated values within the experimental uncertainties.     

Standard‐free composition measurements of Alx In1–xN by low‐loss electron energy loss spectroscopy

We demonstrate a standard‐free method to retrieve compositional information in Al_x In_1–xN thin films by measuring the bulk plasmon energy (E_p), employing electron energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM). Two series of samples were grown by magnetron sputter epitaxy (MSE) and metal organic vapor phase epitaxy (MOVPE), which together cover the full com‐ positional range 0 ≤ x ≤ 1. Complementary compositional measurements were obtained using Rutherford backscattering spectroscopy (RBS) and the lattice parameters were obtained by X‐ray diffraction (XRD). It is shown that E_p follows a linear relation with respect to composition and lattice parameter between the alloying elements from AlN to InN allowing for straightforward compositional analysis. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Experimental (FT‐IR) and theoretical (DFT) studies on prototropy and H‐bond formation for pyrazine‐2‐amidoxime

The results of the first structural studies (with the use of both experimental and theoretical methods) on pyrazine‐2‐amidoxime (PAOX) were shown and discussed. FT‐IR spectra were recorded in different concentrations of the PAOX in apolar solvent to check the possibility of the inter‐ or intramolecular hydrogen‐bond formation. All possible tautomers–rotamers of PAOX were then theoretically considered at the DFT(B3LYP)/6‐311+G** level in vacuo. For selected isomers, calculations were also performed at higher levels of theory {B3LYP/6‐311+G(3df,2p) and G3B3}. Based on the results of DFT calculations, the most stable isomers were found, and their total free energies and infrared spectra were calculated. The energy variation plots for the N8?C7?N9?O10 and N1?C2?C7?N9 dihedral angles were also computed to find two energy barriers, one for E/Z isomerization around the C7?N9 double bond and the other one for rotation of the pyrazinyl ring around the C2?C7 single bond. The results show that the stability of the PAOX isomers strongly depend on their configuration and orientation of the substituents. The possibilities of inter‐ and intramolecular hydrogen bonds were also experimentally and theoretically checked. Finally, a potential of mean force was determined in CHCl₃ for a dimer of PAOX with hexamethylphosphoramide. Both, experimental and theoretical results are in agreement. Copyright © 2016 John Wiley & Sons, Ltd.     

Measurement of M-shell X-ray production cross sections for the element 73 \leqslant Z \leqslant 83 using 5.96 keV photons

Total M-shell X-ray production cross sections (M XRF) of the some elements in the atomic number range were measured at 5.96 keV incident photon energy using a Si(Li) detector. The results are compared with the experimental and theoretical values in the literature.     

Three dimensional (Z‐dependence), collective and individual semi‐empirical formulae for L X‐ray production and ionization cross section by protons impact within corrected ECPSSR theory and updated experimental data: a review

In this paper we propose a new three dimensional semi‐empirical formulae for the deduction of L X‐ray production and ionization cross sections by introducing the dependence on the atomic number of the target, noted as ‘Z‐dependence’. The data are also fitted collectively and separately (for each element) by analytical functions to calculate semi‐empirical cross sections. For this purpose, the corrected ECPSSR model (noted as eCPSSR) and the published experimental data of L_α, L_β and L_γ X‐ray production and L₁, L₂ and L₃ ionization cross sections in the period (1950–2014) are combined to calculate the semi‐empirical ones for a wide range of elements by proton impact. The semi‐empirical cross sections (for the three x‐rays lines L_α, L_β, L_γ and the three sub‐shells L₁, L₂, L₃) are then deduced by fitting the available experimental data normalized to their corresponding theoretical values (using the eCPSSR model) giving a better representation of the experimental data for the individual interpolation. At last, a comparison is made between the three semi‐empirical formulae reported in this work. Copyright © 2016 John Wiley & Sons, Ltd.     

Charge exchange in collisions between heavy low-charged ions

The probabilities and the effective cross sections of collision-induced one-electron charge exchange between singly charged and four-charged heavy Xe, Cs, Ba, Pb, Bi, and U ions at energies E>0.1 keV/u are calculated by a method of multichannel normalization in the impact parameter representation. The cross sections are rather large with a maximum σ_m≈10⁻¹⁵ cm² at relative energies E _m ≈10–30 keV/u. For collision energies E<10 keV/u, the cross sections sharply decrease with growing resonance defect of the reaction. At high energies E>1 MeV/u, the charge exchange proceeds largely by the capture of inner shell electrons of the ionic targets. The charge exchange cross sections calculated for low-charged Xe, Cs, Ba, Pb, Bi, and U ions are compared with available theoretical and experimental data.     

A study of KαL1 X‐ray satellite spectrum of the elements 27 ≤ Z ≤ 31 by photon excitation

K _α X‐ray satellite spectra of Co, Ni, Cu, Zn, and Ga generated by photon excitation are analyzed using a wavelength dispersion spectrometer. Spectra of Ni, Cu, Zn, and Ga are studied for the first time using a LiF420 crystal. Spectrum of Co was studied with LiF200 crystal in second order. K_αL¹ X‐ray satellite energies and relative intensities are measured. The energy shifts relative to diagram line are computed and are compared with theoretical and semi‐empirical values. Dependence of energy shifts and relative intensities on Z and mode of excitation is analyzed.     

Three‐photon absorption properties of a novel symmetrical Carbazole derivative having terminal 1,10‐phenanthroline rings via carbon–nitrogen (C = N) double bond

Three‐photon absorption (3PA) properties of symmetric‐type carbazole derivatives show great potential for application in light‐activated therapy and optical limiting. A novel symmetrical carbazole derivative (abbreviated as POCP) with end‐groups of 1,10‐phenanthroline rings as the donor moieties, chained via carbon–nitrogen (C = N) double bond, has been synthetized and its three photon absorption properties has been also determined by using a Q‐switched Nd: YAG laser pumped with 30 ps pulses at 1064 nm in dimethylformamide. The measurement of 3PA cross‐section of this compound is performed by open aperture Z‐scan and σ_3PA is 481 × 10^–78 cm⁶ ? s²/photon² for the transition S₀ → S₁. The influence of the molecular structure of this compound on three‐photon absorption cross‐sections is discussed micromechanically by Austin model 1 and Zerner's Intermediate Neglect of Differential Overlap/S method. Copyright © 2012 John Wiley & Sons, Ltd.