期刊
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
卷 9, 期 12, 页码 3538-3543出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.8b01429
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资金
- ERC-ADG-2014 - Advanced Investigator Grant under the Horizon 2020 EU Framework Program for Research and Innovation [669531 EDAX]
- Helmholtz-Virtual Institute Dynamic Pathways in Multidimensional Landscapes [VI419]
- Swedish Research Council (VR)
- AMOS program within the Chemical Sciences, Geosciences and Biosciences Division of the Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy
- Volkswagen Foundation [87008]
- DFG [SFB 755, SFB 1073]
- Max Planck Society
- the Knut and Alice Wallenberg Foundation [KAW-2013.0020]
- LCLS
- Stanford University through the Stanford Institute for Materials Energy Sciences (SIMES)
- Lawrence Berkeley National Laboratory (LBNL)
- University of Hamburg through the BMBF [FSP 301]
- Center for Free Electron Laser Science (CFEL)
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.
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