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.
CITATION STYLE
Slavíček, P., Kryzhevoi, N. V., Aziz, E. F., & Winter, B. (2016, January 21). Relaxation Processes in Aqueous Systems upon X-ray Ionization: Entanglement of Electronic and Nuclear Dynamics. Journal of Physical Chemistry Letters. American Chemical Society. https://doi.org/10.1021/acs.jpclett.5b02665
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