Refine
Has Fulltext
- no (11)
Document Type
- Article (11) (remove)
Language
- English (11)
Is part of the Bibliography
- yes (11)
Keywords
- CO desorption (1)
- Density functional theory (1)
- Potential of mean force (1)
- Pump-probe (1)
- Two-temperature model (1)
- X-ray spectroscopy (1)
- anti-Stokes resonant x-ray raman scattering (1)
- excited state selectivity (1)
- free electron lasers (1)
- resonant inelastic x-ray scattering (1)
- ultrafast photochemistry (1)
Institute
Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal-ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. pi-Back-donation is found to be mainly determined by the metal site occupation, whereas the ligand hole instead influences sigma-donation. Our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes.