Ultrafast Transient Absorption Spectroscopy of UO(2)(2+)and [UO2Cl](+)
- For the only water coordinated "free" uranyl (VI) aquo ion in perchlorate solution we identified and assigned several different excited states and showed that the (3)Delta state is the luminescent triplet state from transient absorption spectroscopy. With additional data from other spectroscopic methods (TRLFS, UV/vis) we generated a detailed Jablonski diagram and determined rate constants for several state transitions, like the inner conversion rate constant from the (3)Phi state to the (3)Delta state transition to be 0.35 ps(-1). In contrast to luminescence measurements, it was possible to observe the highly quenched uranyl(VI) ion in highly concentrated chloride solution by TAS and we were able to propose a dynamic quenching mechanism, where chloride complexation is followed by the charge transfer from the excited state uranyl(VI) to chloride. This proposed quenching route is supported by TD-DFT calculations.
Author details: | Toni HaubitzORCiD, Satoru TsushimaORCiD, Robin Steudtner, Björn DrobotORCiD, Gerhard Geipel, Thorsten Stumpf, Michael Uwe KumkeORCiDGND |
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DOI: | https://doi.org/10.1021/acs.jpca.8b05567 |
ISSN: | 1089-5639 |
Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/30095911 |
Title of parent work (English): | The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory |
Publisher: | American Chemical Society |
Place of publishing: | Washington |
Publication type: | Article |
Language: | English |
Year of first publication: | 2018 |
Publication year: | 2018 |
Release date: | 2021/10/04 |
Volume: | 122 |
Issue: | 35 |
Number of pages: | 8 |
First page: | 6970 |
Last Page: | 6977 |
Funding institution: | Federal Ministry for Economic Affairs and Energy [02E11415F] |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
DDC classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
Peer review: | Referiert |