Ab Initio Calculations of X-ray Spectra: Atomic Multiplet and Molecular Orbital Effects in a Multiconfigurational SCF Approach to the L-Edge Spectra of Transition Metal Complexes
Number of Authors: 7
2012 (English)In: Journal of Physical Chemistry Letters, ISSN 1948-7185, E-ISSN 1948-7185, Vol. 3, no 23, 3565-3570 p.Article in journal (Refereed) Published
A new ab initio approach to the calculation of X-ray spectra is demonstrated. It combines a high-level quantum chemical description of the chemical interactions and local atomic multiplet effects. We show here calculated L-edge X-ray absorption (XA) and resonant inelastic X-ray scattering spectra for aqueous Ni2+ and XA spectra for a polypyridyl iron complex. Our quantum chemical calculations on a high level of accuracy in a post-Hartree–Fock framework give excellent agreement with experiment. This opens the door to reliable and detailed information on chemical interactions and the valence electronic structure in 3d transition-metal complexes also in transient excited electronic states. As we combine a molecular-orbital description with a proper treatment of local atomic electron correlation effects, our calculations uniquely allow, in particular, identifying the influence of interatomic chemical interactions versus intra-atomic correlations in the L-edge X-ray spectra.
Place, publisher, year, edition, pages
2012. Vol. 3, no 23, 3565-3570 p.
X-ray spectroscopy, spectrum simulations, resonant inelastic X-ray scattering, RASSCF calculations, transition metal ions
Research subject Physics
IdentifiersURN: urn:nbn:se:su:diva-85227DOI: 10.1021/jz301479jISI: 000312170600029OAI: oai:DiVA.org:su-85227DiVA: diva2:583005
FunderSwedish Research Council