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Title: Disentangling Transient Charge Density and Metal–Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering

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. π-Back-donation is found to be mainly determined by the metal site occupation, whereas the ligand hole instead influences σ-donation. Here, 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.
Authors:
ORCiD logo [1] ; ORCiD logo [2] ;  [3] ;  [4] ; ORCiD logo [5] ;  [4] ;  [4] ;  [6] ;  [6] ;  [6] ;  [6] ;  [7] ;  [6] ;  [6] ;  [8] ; ORCiD logo [6] ;  [6] ;  [9] ;  [10] ; ORCiD logo [11] more »; ORCiD logo [4] ;  [6] ; ORCiD logo [2] ;  [3] « less
  1. Univ. Potsdam, Potsdam (Germany)
  2. Stockholm Univ., Stockholm (Sweden)
  3. Univ. Potsdam, Potsdam (Germany); Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany)
  4. Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany)
  5. Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  7. SLAC National Accelerator Lab., Menlo Park, CA (United States); Univ. of Warwick, Coventry (United Kingdom)
  8. SLAC National Accelerator Lab., Menlo Park, CA (United States); Beijing Normal Univ., Beijing (China)
  9. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); European XFEL, Schenefeld (Germany)
  10. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); Gottingen Univ., Gottingen (Germany)
  11. Uppsala Univ., Uppsala (Sweden); Univ. di Siena, Siena (Italy)
Publication Date:
Report Number(s):
SLAC-PUB-17249
Journal ID: ISSN 1948-7185
Grant/Contract Number:
VI419; SFB 755; SB755 (B03); KAW-2013.0020; 87008; 669531; AC02-76SF00515
Type:
Published Article
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Name: Journal of Physical Chemistry Letters; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1457798
Alternate Identifier(s):
OSTI ID: 1454547