Relaxation Processes in Aqueous Systems upon X-ray Ionization: Entanglement of Electronic and Nuclear Dynamics

  • Slavíček P
  • Kryzhevoi N
  • Aziz E
 et al. 
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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 non-radiative decay of the highly non-equilibrium transients leads to a series of reactive species which have not been considered in any high-energy radiation process in water. Non-local 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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  • Petr Slavíček

  • Nikolai V. Kryzhevoi

  • Emad F. Aziz

  • Bernd Winter

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