The electronic structure of a compound plays a key role in its functionality and hence its applications.The core-level X-ray spectroscopy technique at the metal L-edge is widely used for probing the valence electronic...The electronic structure of a compound plays a key role in its functionality and hence its applications.The core-level X-ray spectroscopy technique at the metal L-edge is widely used for probing the valence electronic structure.The X-ray spectral features in the metal L-edge energy regime are usually complicated by a multitude of interactions,which make them challenging to interpret.The X-ray absorption spectra(XAS)and the resonant inelastic X-ray scattering(RIXS)spectra in the cobalt L-edge energy regime of tris(2,2’-bipyridine)cobalt compounds[Co^(Ⅱ)(bpy)3]^(2+)and[CoⅢ(bpy)3]3+are calculated using an ab initio restricted active space(RAS)approach.The experimental spectra are nicely reproduced and their spectral features are interpreted in terms of the orbital contributions and the final-state contributions.Unbiased assignments on the spin state of the ground state of these two cobalt compounds have been critically assessed through valence-excited state calculations and the fingerprints of the X-ray spectral features together with the calculations of the branching ratio.展开更多
基金support from the National Natural Science Foundation of China(91741105)Chongqing Municipal Natural Science Foundation(cstc2018jcyjAX0625).
文摘The electronic structure of a compound plays a key role in its functionality and hence its applications.The core-level X-ray spectroscopy technique at the metal L-edge is widely used for probing the valence electronic structure.The X-ray spectral features in the metal L-edge energy regime are usually complicated by a multitude of interactions,which make them challenging to interpret.The X-ray absorption spectra(XAS)and the resonant inelastic X-ray scattering(RIXS)spectra in the cobalt L-edge energy regime of tris(2,2’-bipyridine)cobalt compounds[Co^(Ⅱ)(bpy)3]^(2+)and[CoⅢ(bpy)3]3+are calculated using an ab initio restricted active space(RAS)approach.The experimental spectra are nicely reproduced and their spectral features are interpreted in terms of the orbital contributions and the final-state contributions.Unbiased assignments on the spin state of the ground state of these two cobalt compounds have been critically assessed through valence-excited state calculations and the fingerprints of the X-ray spectral features together with the calculations of the branching ratio.
