Relaxation processes in aqueous systems upon X-ray ionization

• Verfasst von: Slavíček, Petr [VerfasserIn]
• Verfasst von: Kryzhevoi, Nikolai V. [VerfasserIn]
• Titel: Relaxation processes in aqueous systems upon X-ray ionization
• Titelzusatz: entanglement of electronic and nuclear dynamics
• Verf.angabe: Petr Slavíček, Nikolai V. Kryzhevoi, Emad F. Aziz, and Bernd Winter
• Jahr: 2016
• Jahr des Originals: 2015
• Umfang: 10 S.
• Fussnoten: Published: December 29, 2015 ; Gesehen am 08.05.2020
• Titel Quelle: Enthalten in: The journal of physical chemistry letters
• Ort Quelle: Washington, DC : ACS, 2010
• Jahr Quelle: 2016
• Band/Heft Quelle: 7(2016), 2, Seite 234-243
• ISSN Quelle: 1948-7185
• DOI: doi:10.1021/acs.jpclett.5b02665
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1697727468

Abstract

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.