Philippe Wernet, T. Leitner, Ida Josefsson, T. Mazza, P. S. Miedema, H. Schroder, Martin Beye, K. Kunnus, S. Schreck, P. Radcliffe, S. Dusterer, M. Meyer, Michael Odelius, Alexander Fohlisch
- We prove the hitherto hypothesized sequential dissociation of Fe(CO)(5) in the gas phase upon photoexcitation at 266 nm via a singlet pathway with time-resolved valence and core-level photoelectron spectroscopy with an x-ray free-electron laser. Valence photoelectron spectra are used to identify free CO molecules and to determine the time constants of stepwise dissociation to Fe(CO)(4) within the temporal resolution of the experiment and further to Fe(CO)(3) within 3 ps. Fe 3p core-level photoelectron spectra directly reflect the singlet spin state of the Fe center in Fe(CO)(5), Fe(CO)(4), and Fe(CO)(3) showing that the dissociation exclusively occurs along a singlet pathway without triplet-state contribution. Our results are important for assessing intra- and intermolecular relaxation processes in the photodissociation dynamics of the prototypical Fe(CO)(5) complex in the gas phase and in solution, and they establish time-resolved core-level photoelectron spectroscopy as a powerful tool for determining the multiplicity of transitionWe prove the hitherto hypothesized sequential dissociation of Fe(CO)(5) in the gas phase upon photoexcitation at 266 nm via a singlet pathway with time-resolved valence and core-level photoelectron spectroscopy with an x-ray free-electron laser. Valence photoelectron spectra are used to identify free CO molecules and to determine the time constants of stepwise dissociation to Fe(CO)(4) within the temporal resolution of the experiment and further to Fe(CO)(3) within 3 ps. Fe 3p core-level photoelectron spectra directly reflect the singlet spin state of the Fe center in Fe(CO)(5), Fe(CO)(4), and Fe(CO)(3) showing that the dissociation exclusively occurs along a singlet pathway without triplet-state contribution. Our results are important for assessing intra- and intermolecular relaxation processes in the photodissociation dynamics of the prototypical Fe(CO)(5) complex in the gas phase and in solution, and they establish time-resolved core-level photoelectron spectroscopy as a powerful tool for determining the multiplicity of transition metals in photochemical reactions of coordination complexes. Published by AIP Publishing.…
Metadaten| Author details: | Philippe WernetORCiD, T. Leitner, Ida Josefsson, T. Mazza, P. S. Miedema, H. Schroder, Martin BeyeORCiDGND, K. Kunnus, S. Schreck, P. Radcliffe, S. Dusterer, M. Meyer, Michael OdeliusORCiD, Alexander FohlischORCiDGND |
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| DOI: | https://doi.org/10.1063/1.4984774 |
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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/28595420 |
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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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| 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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| Year of first publication: | 2017 |
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| Publication year: | 2017 |
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| Release date: | 2020/04/20 |
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| Volume: | 146 |
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| Number of pages: | 5 |
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| Funding institution: | Helmholtz Virtual Institute "Dynamic Pathways in Multidimensional Landscapes"; Volkswagen Stiftung; Swedish Research Council; Carl Trygger Foundation; 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 Research [05K10PK2] |
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| Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Physik und Astronomie |
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| Peer review: | Referiert |
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