Journal Article

PUBDB-2018-05889

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Disentangling Transient Charge Density and Metal–Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering

Jay, R. M. (Corresponding author) ; Norell, J. ; Eckert, S. ; Hantschmann, M. ; Beye, M.DESY* ; Kennedy, B. ; Quevedo, W.Extern* ; Schlotter, W. F. ; Dakovski, G. L. ; Minitti, M. P. ; Hoffmann, M. C.DESY* ; Mitra, A. ; Moeller, S. P. ; Nordlund, D. ; Zhang, W. ; Liang, H. W. ; Kunnus, K. ; Kubiček, K.XFEL.EU* ; Techert, S.DESY* ; Lundberg, M. ; Wernet, P. ; Gaffney, K. ; Odelius, M. ; Föhlisch, A.Extern*

2018
ACS Washington, DC

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Please use a persistent id in citations: doi:10.1021/acs.jpclett.8b01429  doi:10.3204/PUBDB-2018-05889

Abstract: 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. 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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Contributing Institute(s):

1. Strukturdynamik Chemischer Systeme (FS-SCS)
2. FS-FLASH (FS-FLASH)

Research Program(s):

1. 6215 - Soft Matter, Health and Life Sciences (POF3-621) (POF3-621)

Experiment(s):

1. Measurement at external facility

Appears in the scientific report 2018

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Database coverage:
; ; ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; IF >= 5 ; JCR ; NCBI Molecular Biology Database ; SCOPUS ; Science Citation Index ; Science Citation Index Expanded ; Web of Science Core Collection

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