High-resolution manganese X-ray fluorescence spectroscopy. Oxidation-state and spin-state sensitivity

Journal Article · Wed Apr 06 04:00:00 EDT 1994 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00086a024· OSTI ID:7267444

Peng, G; Wang, X; Grush, M M ^[1]; deGroot, F M.F. ^[2]; Hamalainen, K ^[3]; Moore, J A ^[4]; Hastings, J B; Siddons, D P ^[5]; Armstrong, W H ^[6]; Mullins, O C ^[7]; Cramer, S P ^[8]

---

1. Univ. of California, Davis, CA (United States)
2. Univ. of Nijmegen (Netherlands)
3. Univ. of Helsinki (Finland)
4. Lawrence Berkeley Lab., CA (United States)
5. Brookhaven National Lab., Upton, NY (United States)
6. Boston College, MA (United States)
7. Schlumberger-Doll Research, Ridgefield, CT (United States)
8. 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), Journal Name: Journal of the American Chemical Society; (United States) Journal Issue: 7 Vol. 116:7; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
CHEMICAL ANALYSIS
COMPILED DATA
COMPLEXES
DATA
ELECTRONIC STRUCTURE
EMISSION SPECTROSCOPY
FLUORESCENCE SPECTROSCOPY
INFORMATION
LIGANDS
MANGANESE COMPLEXES
NONDESTRUCTIVE ANALYSIS
NUMERICAL DATA
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
VALENCE
X-RAY EMISSION ANALYSIS
X-RAY FLUORESCENCE ANALYSIS