Measured X-ray Absorption Near Edge Structure Spectra Research Articles

Survey of impact glasses in shergottites searching for Martian sulfate using X-ray absorption near-edge structure

The surface of Mars has experienced progressive oxidation, resulting in the formation of sulfate minerals as evidenced from surface exploration missions. However, no clear evidence for the presence of sulfate minerals has been reported within Martian meteorites. This study examined sulfur speciation in impact glasses of three basaltic shergottites, Elephant Moraine (EETA) 79001, Larkman Nunatak (LAR) 06319, and Dhofar 019, using X-ray absorption near-edge structure (XANES) spectroscopy. The measured XANES spectra were classified into four types: (1) sulfide, (2) highly reduced sulfide glass (∼IW+1), (3) mixture of sulfide and sulfate, and (4) sulfate. The sulfate spectra observed from EETA79001 and LAR 06319 were mixed with sulfide from the reduced igneous host rock as impact glasses were formed by shock on the surface of Mars, both sulfide and sulfate would have possibly originated on Mars. Besides, highly reduced sulfide present in the same impact glasses is inconsistent with secondary alteration on the oxic Earth’s environment. In contrast to EETA79001 and LAR 06319, all of the XANES spectra from Dhofar 019 showed the only sulfate, whose origin is most likely from terrestrial alteration. Combining with the geochemical signatures of volatile elements (e.g., D/H, C, and halogens) in impact glasses of EETA79001 and LAR 06319, we propose two possible scenarios for the formation of sulfate species to the shergottite host-rocks: (i) oxidation of sulfide minerals by subsurface oxic water in Mars, or (ii) precipitation of sulfate mineral derived from Martian subsurface water. The difference between the two models is the source of S(VI) species, whether it originated from (i) magmatic sulfide in shergottite or (ii) sulfate ion in the subsurface water/ice. Both models indicate that the ancient (∼4 Ga) water reservoir might have already been oxic, and it requires post-magmatic water–rock interaction that formed sulfate minerals whose oxidized signatures were incorporated into impact glass.

Electronic structure of pristine and Ni-substituted LaFeO3 from near edge x-ray absorption fine structure experiments and first-principles simulations

We present a joint theoretical and experimental study of the oxygen $K$-edge spectra for LaFeO$_3$ and homovalent Ni-substituted LaFeO$_3$ (LaFe$_{0.75}$Ni$_{0.25}$O$_3$), using first-principles simulations based on density-functional theory with extended Hubbard functionals and x-ray absorption near edge structure (XANES) measurements. Ground-state and excited-state XANES calculations employ Hubbard on-site $U$ and inter-site $V$ parameters determined from first principles and the Lanczos recursive method to obtain absorption cross sections, which allows for a reliable description of XANES spectra in transition-metal compounds in a very broad energy range, with an accuracy comparable to that of hybrid functionals but at a substantially lower cost. We show that standard gradient-corrected exchange-correlation functionals fail in capturing accurately the electronic properties of both materials. In particular, for LaFe$_{0.75}$Ni$_{0.25}$O$_3$ they do not reproduce its semiconducting behaviour and provide a poor description of the pre-edge features at the O $K$ edge. The inclusion of Hubbard interactions leads to a drastic improvement, accounting for the semiconducting ground state of LaFe$_{0.75}$Ni$_{0.25}$O$_3$ and for a good agreement between calculated and measured XANES spectra. We show that the partial substitution of Fe for Ni affects the conduction-band bottom by generating a strongly hybridized O($2p$)-Ni($3d$) minority-spin empty electronic state. The present work, based on a consistent correction of self-interaction errors, outlines the crucial role of extended Hubbard functionals to describe the electronic structure of complex transition-metal oxides such as LaFeO$_3$ and LaFe$_{0.75}$Ni$_{0.25}$O$_3$ and paves the way to future studies on similar systems.

Formation and Local Structure Analysis of High‐Valence Chromium Ion in Dicalcium Silicate

Dicalcium silicate (2CaO·SiO2) is a typical silicate compound that exists even at elevated temperatures. Different types of elements can be dispersed in dicalcium silicate to form a solid solution phase. However, the dispersion behavior of transition elements that can display different ionic valences is not well understood. Herein, we investigate the local structure of chromium ions dispersed in dicalcium silicate of different phase states under inert and air atmospheres using Cr K‐edge X‐ray absorption near‐edge structure (XANES) spectroscopy and first‐principle calculations. The measured XANES spectra indicated that Cr ions exist as high‐valence states when dispersed in dicalcium silicate in air atmosphere. Specifically, Cr6+ ions were detected in γ‐dicalcium silicate, which was prepared by annealing a mixture of 2CaO·SiO2 and Cr2O3 at 973 K in air atmosphere. In addition, the XANES spectra obtained via first‐principle calculations revealed that Cr ions, with high‐valence states between Cr4+ and Cr6+, in dicalcium silicate, occupy the tetrahedral Si4+ sites.

An alternative method for an interactive determination of the high-order harmonic ratio in monochromatized X-rays

An alternative method for quantifying the high-order harmonic ratio in monochromatized X-rays was developed and compared with the conventional X-ray absorption near-edge structure (XANES) method. The proposed method can calculate the harmonic ratio interactively from data obtained using two ionization chamber detectors without XANES spectra. For a comparison of the result obtained using this method to that obtained using the conventional one, Zr and Mo K-edge XANES spectra were taken by using the 3rd harmonics included in monochromatized X-rays. These spectra were measured in the transmission mode as a function of detuning in the range of 0–30%. The harmonic ratios for the measured XANES spectra were calculated using both methods. Compared to the conventional method, the results of the alternative method showed slight differences that were within experimental errors, except at edge regions. Therefore, the proposed method can give a correct harmonic ratio when using only one data point. Thus, the proposed method greatly simplifies the task of estimating high-order harmonic ratios.

Multiple Scattering Approach to Pt L3-edge X-Ray Absorption near Edge Structure Spectra of Small Pt Clusters with Hydrogen Adsorption

Recent experimental studies on the Pt L-edge X-ray absorption near edge structure (XANES) spectra of Pt clusters show that the spectra are greatly influenced by hydrogen adsorption. In this paper the full multiple scattering method, which we developed, is applied to study the difference in measured XANES spectra before and after the hydrogen adsorption. Hydrogen atoms are more plausible on adsorbed sites out of the cluster than on absorbed sites inside the cluster though the calculated spectra are not so sensitive to the adsorption sites. The adsorbed hydrogen atoms have rather negative charge due to the charge transfer from Pt atoms. In the charge transfer process Pt 6s (or 6p) electrons play a more important role than 5d electrons. Furthermore the small difference in the XANES spectra for Pt foil and small cluster is studied, and we find that it is due to the large fraction of surface Pt atoms in the latter system.

A Xanes Study of Square Copper(II) Complexes

AbstractThe XANES (X-ray absorption near edge structure) spectra of copper(II) ions in solid state and in solution of the square-planar copper(II) complexes with tetraaza macrocycles were measured. The peaks in the measured XANES spectra shifted to lower energy side with increasing the electron density of central copper(II) ions. The molecular orbital calculations for the complexes were carried out by the DV-Xα method, and the theoretical XANES spectra were estimated. The clear chemical shift obtained by this XANES study is evaluated and leads to a new concept of π-back donation between the copper(II) complexes and counter anion in aqueous solution.