High-resolution manganese X-ray fluorescence spectroscopy. Oxidation-state and spin-state sensitivity
- Univ. of California, Davis, CA (United States)
- Univ. of Nijmegen (Netherlands)
- Univ. of Helsinki (Finland)
- Lawrence Berkeley Lab., CA (United States)
- Brookhaven National Lab., Upton, NY (United States)
- Boston College, MA (United States)
- Schlumberger-Doll Research, Ridgefield, CT (United States)
- Univ. of California, Davis, CA (United States) Lawrence Berkeley Lab., CA (United States)
K,[beta] X-ray emission spectra have been recorded for Mn(II), Mn(III), and Mn(IV) compounds with a variety of ligands. The spectra have been interpreted and simulated as atomic multiplets perturbed by a crystal field. The X-ray fluorescence in this region, which results from 3p [yields] 1s transitions, is split between a strong K,[beta][sub 1.3] region and a weaker K[beta][prime] satellite. For Mn(II) complexes, the K[beta][prime] region derives from final states with antiparallel net spins between the 3p[sup 5] hole and the 3d[sup 5] valence shell. The K[beta][sub 1,3] region is dominated by spin-parallel final states. For octahedral high-spin Mn(II), Mn(III), and Mn(IV) complexes, the K,[beta][sub 1.3] peak position shift to lower energy with increasing oxidation state. The K[beta][prime] feature is weaker and broader for the higher oxidation states, and it is almost unobservable for low-spin Mn(III). K[beta] fluorescence is a good probe of Mn spin state and oxidation state. Spin-selective X-ray absorption near-edge spectra, taken by monitoring specific K[beta] features, are illustrated. The potential for site-selective absorption spectroscopy, based on monitoring chemically sensitive K[beta] features, is discussed. 29 refs., 6 figs., 1 tab.
- OSTI ID:
- 7267444
- Journal Information:
- Journal of the American Chemical Society; (United States), Vol. 116:7, Issue 7; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
Similar Records
High resolution x-ray fluorescence spectroscopy - a new technique for site- and spin-selectivity
Spin selective x-ray absorption spectroscopy: Demonstration using high resolution Fe [ital K][beta] fluorescence
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
MANGANESE COMPLEXES
ELECTRONIC STRUCTURE
FLUORESCENCE SPECTROSCOPY
X-RAY FLUORESCENCE ANALYSIS
COMPILED DATA
LIGANDS
VALENCE
CHEMICAL ANALYSIS
COMPLEXES
DATA
EMISSION SPECTROSCOPY
INFORMATION
NONDESTRUCTIVE ANALYSIS
NUMERICAL DATA
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
X-RAY EMISSION ANALYSIS
400201* - Chemical & Physicochemical Properties
400102 - Chemical & Spectral Procedures