High-Resolution Manganese X-ray Fluorescence Spectroscopy. Oxidation-State and Spin-State Sensitivity

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.