X-ray Absorption and Emission Spectroscopy of CrIII (Hydr)Oxides: Analysis of the K-Pre-Edge Region

被引：20

作者：

Frommer, Jakob ^{[2
]}

Nachtegaal, Maarten ^{[1
]}

Czekaj, Izabela ^{[1
]}

Weng, Tsu-Chien ^{[3
]}

Kretzschmar, Ruben ^{[2
]}

机构：

[1] Paul Scherrer Inst, Gen Energy Res Dept, CH-5232 Villigen, Switzerland

[2] ETH, Inst Biogeochem & Pollutant Dynam, CH-8092 Zurich, Switzerland

[3] European Synchrotron Radiat Facil, F-38043 Grenoble, France

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2009年 / 113卷 / 44期

关键词：

MINERALS; CHROMIUM; SPECIATION; SCATTERING; SPECTRA; OXYGEN; COORDINATION; FE; MANGANESE; GEOMETRY;

D O I：

10.1021/jp902604p

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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 Lip new opportunities for investigating the local coordination environment of chromium in poorly ordered solids of environmental relevance

引用

页码：12171 / 12178

页数：8

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