T. Leitner, Ida Josefsson, T. Mazza, Piter S. Miedema, H. Schröder, Martin Beye, Kristjan Kunnus, S. Schreck, Stefan Düsterer, Alexander Föhlisch, M. Meyer, Michael Odelius, Philippe Wernet
- The prototypical photoinduced dissociation of Fe(CO)(5) in the gas phase is used to test time-resolved x-ray photoelectron spectroscopy for studying photochemical reactions. Upon one-photon excitation at 266 nm, Fe(CO)(5) successively dissociates to Fe(CO)(4) and Fe(CO)(3) along a pathway where both fragments retain the singlet multiplicity of Fe(CO)(5). The x-ray free-electron laser FLASH is used to probe the reaction intermediates Fe(CO)(4) and Fe(CO)(3) with time-resolved valence and core-level photoelectron spectroscopy, and experimental results are interpreted with ab initio quantum chemical calculations. Changes in the valence photoelectron spectra are shown to reflect changes in the valenceorbital interactions upon Fe-CO dissociation, thereby validating fundamental theoretical concepts in Fe-CO bonding. Chemical shifts of CO 3 sigma inner-valence and Fe 3 sigma core-level binding energies are shown to correlate with changes in the coordination number of the Fe center. We interpret this with coordination-dependent chargeThe prototypical photoinduced dissociation of Fe(CO)(5) in the gas phase is used to test time-resolved x-ray photoelectron spectroscopy for studying photochemical reactions. Upon one-photon excitation at 266 nm, Fe(CO)(5) successively dissociates to Fe(CO)(4) and Fe(CO)(3) along a pathway where both fragments retain the singlet multiplicity of Fe(CO)(5). The x-ray free-electron laser FLASH is used to probe the reaction intermediates Fe(CO)(4) and Fe(CO)(3) with time-resolved valence and core-level photoelectron spectroscopy, and experimental results are interpreted with ab initio quantum chemical calculations. Changes in the valence photoelectron spectra are shown to reflect changes in the valenceorbital interactions upon Fe-CO dissociation, thereby validating fundamental theoretical concepts in Fe-CO bonding. Chemical shifts of CO 3 sigma inner-valence and Fe 3 sigma core-level binding energies are shown to correlate with changes in the coordination number of the Fe center. We interpret this with coordination-dependent charge localization and core-hole screening based on calculated changes in electron densities upon core-hole creation in the final ionic states. This extends the established capabilities of steady-state electron spectroscopy for chemical analysis to time-resolved investigations. It could also serve as a benchmark for howcharge and spin density changes in molecular dissociation and excited-state dynamics are expressed in valence and core-level photoelectron spectroscopy. Published by AIP Publishing.…
MetadatenAuthor details: | T. Leitner, Ida JosefssonORCiD, T. Mazza, Piter S. MiedemaORCiD, H. Schröder, Martin BeyeORCiD, Kristjan KunnusORCiD, S. Schreck, Stefan DüstererORCiDGND, Alexander FöhlischORCiDGND, M. Meyer, Michael OdeliusORCiD, Philippe WernetORCiD |
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DOI: | https://doi.org/10.1063/1.5035149 |
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ISSN: | 0021-9606 |
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ISSN: | 1089-7690 |
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Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/30068152 |
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Title of parent work (English): | The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr |
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Subtitle (English): | Photoelectron spectra of Fe(CO)(5), Fe(CO)(4), and Fe(CO)(3) |
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Publisher: | American Institute of Physics |
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Place of publishing: | Melville |
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Publication type: | Article |
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Language: | English |
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Date of first publication: | 2018/07/27 |
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Publication year: | 2018 |
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Release date: | 2021/10/28 |
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Volume: | 149 |
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Issue: | 4 |
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Number of pages: | 12 |
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Funding institution: | Helmholtz Virtual Institute; Volkswagen StiftungVolkswagen; Swedish Research Council (V.R.)Swedish Research Council; Lennander Foundation; excellence cluster "The Hamburg Center for Ultrafast Imaging-Structure, Dynamics, and Control of Matter at the Atomic Scale" of the Deutsche Forschungsgemeinschaft (CUI) [DFG-EXC1074]; German Federal Ministry of Education and ResearchFederal Ministry of Education & Research (BMBF); [05K10PK2] |
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Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Physik und Astronomie |
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DDC classification: | 5 Naturwissenschaften und Mathematik / 53 Physik / 530 Physik |
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Peer review: | Referiert |
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Publishing method: | Open Access / Green Open-Access |
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