Photochemical activation of carbon dioxide in Mg+(CO2)(H2O)0,1
© The Author(s) 2020.
| Veröffentlicht in: | Theoretical chemistry accounts. - 1998. - 139(2020), 8 vom: 12., Seite 127 |
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| 1. Verfasser: | |
| Weitere Verfasser: | , , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2020
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| Zugriff auf das übergeordnete Werk: | Theoretical chemistry accounts |
| Schlagworte: | Journal Article Carbon dioxide activation Multi-reference calculations Photoactivation Spectroscopy |
| Zusammenfassung: | © The Author(s) 2020. We combine multi-reference ab initio calculations with UV-VIS action spectroscopy to study photochemical activation of CO2 on a singly charged magnesium ion, [MgCO2(H2O)0,1]+, as a model system for the metal/ligand interactions relevant in CO2 photochemistry. For the non-hydrated species, two separated Mg+ 3s-3p bands are observed within 5.0 eV. The low-energy band splits upon hydration with one water molecule. [Mg(CO2)]+ decomposes highly state-selectively, predominantly via multiphoton processes. Within the low-energy band, CO2 is exclusively lost within the excited state manifold. For the high-energy band, an additional pathway becomes accessible: the CO2 ligand is activated via a charge transfer, with photochemistry taking place on the CO2 - moiety eventually leading to a loss of CO after absorption of a second photon. Upon hydration, already excitation into the first and second excited state leads to CO2 activation in the excited state minimum; however, CO2 predominantly evaporates upon fluorescence or absorption of another photon |
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| Beschreibung: | Date Revised 29.03.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1432-881X |
| DOI: | 10.1007/s00214-020-02640-w |