X-ray absorption and emission spectroscopy of Cr(III) (hydr)oxides: analysis of the K-pre-edge region.
Pre-edge spectral features below the main X-ray absorption K-edge of transition metals show a pronounced chemical sensitivity and are promising sources of structural information. Nevertheless, the use of pre-edge analysis in applied research is limited because of the lack of definite theoretical peak-assignments. The aim of this study was to determine the factors affecting the chromium K-pre-edge features in trivalent chromium-bearing oxides and oxyhydroxides. The selected phases varied in the degree of octahedral polymerization and the degree of iron-for-chromium substitution in the crystal structure. We investigated the pre-edge fine structure by means of high-energy-resolution fluorescence detected X-ray absorption spectroscopy and by 1s2p resonant X-ray emission spectroscopy. Multiplet theory and full multiple-scattering calculations were used to analyze the experimental data. We show that the chromium K-pre-edge contains localized and nonlocalized transitions. Contributions arising from nonlocalized metal-metal transitions are sensitive to the nearest metal type and to the linkage mode between neighboring metal octahedra. Analyzing these transitions opens up new opportunities for investigating the local coordination environment of chromium in poorly ordered solids of environmental relevance.
Frommer
Jakob
J
Institute of Biogeochemistry and Pollutant Dynamics, ETH Zurich, CHN F23.2 Universitätstrasse 16, 8092 Zürich, Switzerland.
Nachtegaal
Maarten
M
Czekaj
Izabela
I
Weng
Tsu-Chien
TC
Kretzschmar
Ruben
R
D000042:Absorption; D002412:Cations; D002857:Chromium / Q000032:analysis* / Q000737:chemistry*; D007501:Iron / Q000032:analysis / Q000737:chemistry; D015394:Molecular Structure; D010087:Oxides / Q000032:analysis* / Q000737:chemistry*; D013052:Spectrometry, X-Ray Emission; D056928:X-Ray Absorption Spectroscopy
D002412:Cations; D010087:Oxides; D002857:Chromium; D007501:Iron