Raphael M. Jay, Jesper Norell, Sebastian Eckert, Markus Hantschmann, Martin Beye, Brian Kennedy, Wilson Quevedo, William F. Schlotter, Georgi L. Dakovski, Michael P. Minitti, Matthias C. Hoffmann, Ankush Mitra, Stefan P. Moeller, Dennis Nordlund, Wenkai Zhang, Huiyang W. Liang, Kristian Kunnus, Katharina Kubicek, Simone A. Techert, Marcus Lundberg, Philippe Wernet, Kelly Gaffney, Michael Odelius, Alexander Föhlisch
- 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 excitedSoft 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.…
MetadatenVerfasserangaben: | Raphael M. JayORCiD, Jesper NorellORCiD, Sebastian EckertORCiDGND, Markus HantschmannORCiDGND, Martin BeyeORCiD, Brian Kennedy, Wilson Quevedo, William F. Schlotter, Georgi L. Dakovski, Michael P. Minitti, Matthias C. HoffmannORCiD, Ankush Mitra, Stefan P. Moeller, Dennis NordlundORCiD, Wenkai Zhang, Huiyang W. LiangORCiD, Kristian Kunnus, Katharina Kubicek, Simone A. Techert, Marcus LundbergORCiD, Philippe Wernet, Kelly GaffneyORCiD, Michael OdeliusORCiD, Alexander FöhlischORCiDGND |
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DOI: | https://doi.org/10.1021/acs.jpclett.8b01429 |
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ISSN: | 1948-7185 |
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Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/29888918 |
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Titel des übergeordneten Werks (Englisch): | The journal of physical chemistry letters |
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Verlag: | American Chemical Society |
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Verlagsort: | Washington |
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Publikationstyp: | Wissenschaftlicher Artikel |
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Sprache: | Englisch |
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Datum der Erstveröffentlichung: | 21.06.2018 |
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Erscheinungsjahr: | 2018 |
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Datum der Freischaltung: | 19.11.2021 |
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Band: | 9 |
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Ausgabe: | 12 |
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Seitenanzahl: | 11 |
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Erste Seite: | 3538 |
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Letzte Seite: | 3543 |
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Fördernde Institution: | 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)Swedish Research Council; AMOS program within the Chemical Sciences, Geosciences and Biosciences Division of the Office of Basic Energy Sciences, Office of Science, U.S. Department of EnergyUnited States Department of Energy (DOE); Volkswagen FoundationVolkswagen [87008]; DFGGerman Research Foundation (DFG) [SFB 755, SFB 1073]; Max Planck SocietyMax Planck Society; the Knut and Alice Wallenberg FoundationKnut & 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) |
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Organisationseinheiten: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Physik und Astronomie |
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DDC-Klassifikation: | 5 Naturwissenschaften und Mathematik / 53 Physik / 530 Physik |
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Peer Review: | Referiert |
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Publikationsweg: | Open Access / Hybrid Open-Access |
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