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
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- 作者：Ida Josefsson ; Kristjan Kunnus ; Simon Schreck ; Alexander F枚hlisch ; Frank de Groot ; Philippe Wernet ; Michael Odelius
- 刊名：The Journal of Physical Chemistry Letters
- 出版年：2012
- 出版时间：December 6, 2012
- 年：2012
- 卷：3
- 期：23
- 页码：3565-3570
- 全文大小：316K
- 年卷期：v.3,no.23(December 6, 2012)
- ISSN：1948-7185
文摘
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鈥揊ock 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.