skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: The absorption indicatrix as an empirical model to describe anisotropy in X-ray absorption spectra of pyroxenes
Abstract Anisotropic absorption in crystals is routinely observed in many spectroscopic methods and is recognized in visible light optics as pleochroism in crystalline materials. As with other spectrosco-pies, anisotropy in Fe K-edge X-ray absorption spectroscopy (XAS) can serve both as an indicator of the general structural arrangement and as a conundrum in quantifying the proportions of absorbers in crystals. In materials containing multiple absorbers, observed anisotropies can typically be represented by a linear relationship between measured spectroscopic peak intensities and relative absorber concentrations. In this study, oriented XAS analysis of pyroxenes demonstrates that the macroscopic theory that describes visible light absorption anisotropy of triaxially anisotropic materials can also be applied to X-ray absorption in pyroxenes, as long as the orientation and magnitude of the characteristic absorption vectors are known for each energy. Oriented single-crystal XAS analysis of pyroxenes also shows that the measured magnitude of characteristic absorption axes at a given orientation is energy-dependent and cannot be reproduced by linear combination of intermediate spectra. Although the macroscopic model describes a majority of the anisotropy, there is distinct discordance between the observed and interpolated spectra in the pre-edge between 7109 and 7115 eV, which is marked by spikes in RMSE/mean intensity ratio. Absorption indicatrices for samples analyzed in the visible and at X-ray wavelengths are modeled with a three-dimensional (3D) pedal surface, which functions as an empirical way of interpolating between the observed absorption data. This surface only requires a maximum of three coefficients, and results from the summation of 3D lemniscates. An absorption indicatrix model can be used to characterize anisotropic absorption in crystals and provides a way of comparing XAS spectra from randomly oriented crystals, such as those from polished sections, to a database of characterized crystals.  more » « less
Award ID(s):
1754261 1754268 2042421
PAR ID:
10325062
Author(s) / Creator(s):
; ; ; ;
Publisher / Repository:
American Mineralogist
Date Published:
Journal Name:
American Mineralogist
Volume:
107
Issue:
4
ISSN:
0003-004X
Page Range / eLocation ID:
654 to 663
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; (, Geological Society of America)
    A set of 11 clinoamphibole standards with known Fe3+/ΣFe were analyzed for X-ray absorption spectra at the Advanced Photon Source at Argonne National Laboratory. Fe3+/ΣFe of each sample is known from Mössbauer data, and span from 0% to 100% Fe3+/ΣFe. Due to the extreme absorption anisotropy of crystals, we determined the orientation of clinoamphiboles crystals using single-crystal X-ray diffraction and spindle stage techniques. Clinoamphiboles crystal were then analyzed with the beam propagation and polarization axes along known direction relative to the crystallographic basis. Absorption anisotropy was then interpolated to predict the range of absorption magnitudes a clinoamphibole may exhibit at each energy. Partial least square fits for Fe3+/ΣFe indicate predictions are closest to the known Fe3+/ΣFe when comparing the same orientation of each sample in the dataset. Predictions including all orientations, while less accurate, still yield strong results with an R-squared of 0.9 and RMSE of 4.7. The results from this dataset demonstrate the efficacy of XAS as a microanalytical technique for crystalline materials, and functions as a reference dataset to research in oxybarometry. 
    more » « less
  2. ; ; ; ; ; ; ; ; ; ; et al (, Chemistry of Materials)
    Low-dimensional materials with chain-like (one-dimensional) or layered (two-dimensional) structures are of significant interest due to their anisotropic electrical, optical, and thermal properties. One material with a chain-like structure, BaTiS3 (BTS), was recently shown to possess giant in-plane optical anisotropy and glass-like thermal conductivity. To understand the origin of these effects, it is necessary to fully characterize the optical, thermal, and electronic anisotropy of BTS. To this end, BTS crystals with different orientations (a- and c-axis orientations) were grown by chemical vapor transport. X-ray absorption spectroscopy was used to characterize the local structure and electronic anisotropy of BTS. Fourier transform infrared reflection/transmission spectra show a large in-plane optical anisotropy in the a-oriented crystals, while the c-axis oriented crystals were nearly isotropic in-plane. BTS platelet crystals are promising uniaxial materials for infrared optics with their optic axis parallel to the c-axis. The thermal conductivity measurements revealed a thermal anisotropy of ∼4.5 between the c- and a-axis. Time-domain Brillouin scattering showed that the longitudinal sound speed along the two axes is nearly the same, suggesting that the thermal anisotropy is a result of different phonon scattering rates. 
    more » « less
  3. ; ; ; ; ; ; ; ; ; (, Journal of Physics: Condensed Matter)
    Abstract Strained materials can exhibit drastically modified physical properties in comparison to their fully relaxed analogues. We report on the x-ray absorption spectra (XAS) and magnetic circular dichroism (XMCD) of a strained NiFe 2 O 4 inverse spinel film grown on a symmetry matched single crystal MgGa 2 O 4 substrate. The Ni XAS spectra exhibit a sizable difference in the white line intensity for measurements with the x-ray electric field parallel to the film plane (normal incidence) vs when the electric field is at an angle (off-normal). A considerable difference is also observed in the Fe L 2,3 XMCD spectrum. Modeling of the XAS and XMCD spectra indicate that the modified energy ordering of the cation 3 d states in the strained film leads to a preferential filling of 3 d states with out-of-plane character. In addition, the results point to the utility of x-ray spectroscopy in identifying orbital populations even with elliptically polarized x-rays. 
    more » « less
  4. ; ; ; ; ; ; (, Proceedings of the National Academy of Sciences)
    X-ray absorption spectroscopy (XAS) is a powerful experimental technique to probe the local order in materials with core electron excitations. Experimental interpretation requires supporting theoretical calculations. For water, these calculations are very demanding and, to date, could only be done with major approximations that limited the accuracy of the calculated spectra. This prompted an intense debate on whether a substantial revision of the standard picture of tetrahedrally bonded water was necessary to improve the agreement of theory and experiment. Here, we report a first-principles calculation of the XAS of water that avoids the approximations of prior work, thanks to recent advances in electron excitation theory. The calculated XAS spectra, and their variation with changes of temperature and/or with isotope substitution, are in good quantitative agreement with experiments. The approach requires accurate quasiparticle wave functions beyond density functional theory approximations, accounts for the dynamics of quasiparticles, and includes dynamic screening as well as renormalization effects due to the continuum of valence-level excitations. The three features observed in the experimental spectra are unambiguously attributed to excitonic effects. The preedge feature is associated with a bound intramolecular exciton, the main-edge feature is associated with an exciton localized within the coordination shell of the excited molecule, and the postedge feature is delocalized over more distant neighbors, as expected for a resonant state. The three features probe the local order at short, intermediate, and longer range relative to the excited molecule. The calculated spectra are fully consistent with a standard tetrahedral picture of water. 
    more » « less
  5. ; ; (, The Journal of Chemical Physics)
    X-ray absorption spectroscopy (XAS) is a powerful experimental tool to probe the local structure in materials with the core hole excitations. Here, the oxygen K-edge XAS spectra of the NaCl solution and pure water are computed by using a recently developed GW-Bethe-Salpeter equation approach, based on configurations modeled by path-integral molecular dynamics with the deep-learning technique. The neural network is trained on ab initio data obtained with strongly constrained and appropriately normed density functional theory. The observed changes in the XAS features of the NaCl solution, compared to those of pure water, are in good agreement between experimental and theoretical results. We provided detailed explanations for these spectral changes that occur when NaCl is solvated in pure water. Specifically, the presence of solvating ion pairs leads to localization of electron-hole excitons. Our theoretical XAS results support the theory that the effects of the solvating ions on the H-bond network are mainly confined within the first hydration shell of ions, however beyond the shell the arrangement of water molecules remains to be comparable to that observed in pure water. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email