Unoccupied states of pyrite probed by electron energy-loss spectroscopy (EELS)
-
Laurence A.J. Garvie
and
Peter R. Buseck
Abstract
Electron energy-loss spectra (EELS) of pyrite (FeS2) were acquired and include the Fe K, L2,3, M2,3, and M1 edges, and the S K, L2,3, and L1 edges. The core-loss edges exhibit a range of shapes and different theories are required to understand the spectra. In the process a clear picture of the conduction-band states as a function of energy above the band gap is obtained. This analysis reveals the extent of mixing of unoccupied states and thus provides an understanding of the limits of interpreting core-loss edges in light of the optical dipole limit. A unified picture of the unoccupied states is obtained by aligning the spectra on a common energy scale relative to the published Bremsstrahlung isochromat spectrum (BIS) and with the results of band structure calculations. This alignment allows similarities between the spectra of different atoms to be related to mixing of local conduction-band states. The coincidence of the Fe K and S L2,3 spectral features attests to the strong hybridization of the Fe p-S 3d states. The main Fe L2,3 edges are followed by structures that confirm an Fe-S bond with a substantial degree of mixing between Fe d6 and d7 states. The aligned EELS spectra clearly divide the unoccupied states into two regions. The first region is dominated by the intense d-like component of the Fe L3 edge and p-like components of the S K and L1 edges. A small pre-peak at the Fe K edge aligned with the Fe L2,3 edge peak maximum is indicative of Fe 4p + 3d eg and S 3p mixing. Similarly, the pre-peak to the S L2,3 edge arises from transitions to states with mixed S s + p + Fe 3d eg character.
© 2015 by Walter de Gruyter Berlin/Boston
Articles in the same Issue
- A zero-damage model for fission-track annealing in zircon
- Unoccupied states of pyrite probed by electron energy-loss spectroscopy (EELS)
- Tugtupite: High-temperature structures obtained from in situ synchrotron diffraction and Rietveld refinements
- SIMS microanalyses for Au in silicates
- Geochemistry of oxide minerals of Nb, Ta, Sn, and Sb in the Varuträsk granitic pegmatite, Sweden: The case of an “anomalous” columbite-tantalite trend
- An X-ray and electron microprobe study of Fe, Ni, Ga, and Ge distribution and local structure in a section of the Canyon Diablo iron meteorite
- Mineralogical approaches to fundamental crystal dissolution kinetics
- Cu L3X-ray absorption spectroscopy and the electronic structure of minerals: Spectral variations in non-stoichiometric bornites, Cu5FeS4
- A new nondestructive X-ray method for the determination of the 3D mineralogy at the micrometer scale
- Dissolution rates and pit morphologies of rhombohedral carbonate minerals
- The effect of TiO2on Pd, Ni, and Fe solubilities in silicate melts
- X-ray absorption spectroscopic study of Fe reference compounds for the analysis of natural sediments
- A survey of hydrous species and concentrations in igneous feldspars
- Structure and crystallization behavior of the (Ba,Sr)HAsO4·H2O solid-solution in aqueous environments
- The crystal structure of painite CaZrB[Al9O18] revisited
- Model pyroxenes II: Structural variation as a function of tetrahedral rotation
- Mn-rich fluorapatite from Austria: Crystal structure, chemical analysis, and spectroscopic investigations
- Isothermal equation of state and compressional behavior of tetragonal edingtonite
- Synthesis and crystal-chemistry of Na(NaMg)Mg5Si8O22(OH)2, a P21/m amphibole
- A single-crystal study on the pressure behavior of phlogopite and petrological implications
- Quantitative electron microprobe analysis of Fe3+/ΣFe: Basic concepts and experimental protocol for glasses
Articles in the same Issue
- A zero-damage model for fission-track annealing in zircon
- Unoccupied states of pyrite probed by electron energy-loss spectroscopy (EELS)
- Tugtupite: High-temperature structures obtained from in situ synchrotron diffraction and Rietveld refinements
- SIMS microanalyses for Au in silicates
- Geochemistry of oxide minerals of Nb, Ta, Sn, and Sb in the Varuträsk granitic pegmatite, Sweden: The case of an “anomalous” columbite-tantalite trend
- An X-ray and electron microprobe study of Fe, Ni, Ga, and Ge distribution and local structure in a section of the Canyon Diablo iron meteorite
- Mineralogical approaches to fundamental crystal dissolution kinetics
- Cu L3X-ray absorption spectroscopy and the electronic structure of minerals: Spectral variations in non-stoichiometric bornites, Cu5FeS4
- A new nondestructive X-ray method for the determination of the 3D mineralogy at the micrometer scale
- Dissolution rates and pit morphologies of rhombohedral carbonate minerals
- The effect of TiO2on Pd, Ni, and Fe solubilities in silicate melts
- X-ray absorption spectroscopic study of Fe reference compounds for the analysis of natural sediments
- A survey of hydrous species and concentrations in igneous feldspars
- Structure and crystallization behavior of the (Ba,Sr)HAsO4·H2O solid-solution in aqueous environments
- The crystal structure of painite CaZrB[Al9O18] revisited
- Model pyroxenes II: Structural variation as a function of tetrahedral rotation
- Mn-rich fluorapatite from Austria: Crystal structure, chemical analysis, and spectroscopic investigations
- Isothermal equation of state and compressional behavior of tetragonal edingtonite
- Synthesis and crystal-chemistry of Na(NaMg)Mg5Si8O22(OH)2, a P21/m amphibole
- A single-crystal study on the pressure behavior of phlogopite and petrological implications
- Quantitative electron microprobe analysis of Fe3+/ΣFe: Basic concepts and experimental protocol for glasses
