Relaxation processes in aqueous systems upon X-ray ionization: entanglement of electronic and nuclear dynamics
The knowledge of primary processes following the interaction of high-energy radiation with molecules in liquid phase is rather limited. In the present Perspective, we report on a newly discovered type of relaxation process involving simultaneous autoionization and proton transfer between adjacent mo...
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| Main Authors: | , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
2016
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| In: |
The journal of physical chemistry letters
Year: 2015, Volume: 7, Issue: 2, Pages: 234-243 |
| ISSN: | 1948-7185 |
| DOI: | 10.1021/acs.jpclett.5b02665 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acs.jpclett.5b02665
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| Author Notes: | Petr Slavíček, Nikolai V. Kryzhevoi, Emad F. Aziz, and Bernd Winter |
| Summary: | The knowledge of primary processes following the interaction of high-energy radiation with molecules in liquid phase is rather limited. In the present Perspective, we report on a newly discovered type of relaxation process involving simultaneous autoionization and proton transfer between adjacent molecules, so-called proton transfer mediated charge separation (PTM-CS) process. Within PTM-CS, transients with a half-transferred proton are formed within a few femtoseconds after the core-level ionization event. Subsequent nonradiative decay of the highly nonequilibrium transients leads to a series of reactive species, which have not been considered in any high-energy radiation process in water. Nonlocal electronic decay processes are surprisingly accelerated upon proton dynamics. Such strong coupling of electronic and nuclear dynamics is a general phenomenon for hydrogen-bonded systems, however, its probability correlates strongly with hydration geometry. We suggest that the newly observed processes will impact future high-energy radiation-chemistry-relevant modeling, and we envision application of autoionization spectroscopy for identification of solution structure details. |
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| Item Description: | Published: December 29, 2015 Gesehen am 08.05.2020 |
| Physical Description: | Online Resource |
| ISSN: | 1948-7185 |
| DOI: | 10.1021/acs.jpclett.5b02665 |