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Disentangling Transient Charge Density and Metal-Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering
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2018 (English)In: Journal of Physical Chemistry Letters, ISSN 1948-7185, E-ISSN 1948-7185, Vol. 9, no 12, p. 3538-3543Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2018. Vol. 9, no 12, p. 3538-3543
National Category
Physical Chemistry
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URN: urn:nbn:se:uu:diva-357208DOI: 10.1021/acs.jpclett.8b01429ISI: 000436382400057OAI: oai:DiVA.org:uu-357208DiVA, id: diva2:1238498
Funder
EU, Horizon 2020, 669531 EDAXSwedish Research CouncilKnut and Alice Wallenberg Foundation, KAW-2013.0020Available from: 2018-08-13 Created: 2018-08-13 Last updated: 2018-09-13Bibliographically approved

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Lundberg, Marcus

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