Biomolecular radiation damage is largely mediated by radicals and low-energy electrons formed by water ionization rather than by direct ionization of biomolecules. It was speculated that such an extensive, localized water ionization can be caused by ultrafast processes following excitation by core-level ionization of hydrated metal ions. In this model, ions relax via a cascade of local Auger-Meitner and, importantly, non-local charge- and energy-transfer processes involving the water environment. Here, we experimentally and theoretically show that, for solvated paradigmatic intermediate-mass Al3+ ions, electronic relaxation involves two sequential solute-solvent electron transfer-mediated decay processes. The electron transfer-mediated decay steps correspond to sequential relaxation from Al5+ to Al3+ accompanied by formation of four ionized water molecules and two low-energy electrons. Such charge multiplication and the generated highly reactive species are expected to initiate cascades of radical reactions.

Center for Free Electron Laser Science DESY Hamburg Germany

Department of Physical Chemistry University of Chemistry and Technology Prague Czech Republic

Department of Physics and Astronomy Uppsala University Uppsala Sweden

Fritz Haber Institut der Max Planck Gesellschaft Berlin Germany

FS BIG DESY Hamburg Germany

Institut für Kernphysik Goethe Universität Frankfurt am Main Frankfurt am Main Germany

Institute for Electronic Structure Dynamics Helmholtz Zentrum Berlin für Materialien und Energie Berlin Germany

MAX 4 Laboratory Lund University Lund Sweden

Synchrotron SOLEIL L'Orme des Merisiers Saint Aubin Paris France

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