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- Title
Photochemical activation of carbon dioxide in Mg<sup>+</sup>(CO<sub>2</sub>)(H<sub>2</sub>O)<sub>0,1</sub>.
- Authors
Pascher, Tobias F.; Barwa, Erik; van der Linde, Christian; Beyer, Martin K.; Ončák, Milan
- Abstract
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.
- Subjects
CARBON dioxide; MULTIPHOTON processes; EXCITED states; LIGHT absorption; MAGNESIUM ions; MAGNESIUM
- Publication
Theoretical Chemistry Accounts: Theory, Computation, & Modeling, 2020, Vol 139, Issue 8, pN.PAG
- ISSN
1432-881X
- Publication type
Article
- DOI
10.1007/s00214-020-02640-w