Charge transfer between molecules lies at the heart of many chemical processes. Here, we focus on the ultrafast electron dynamics associated with the formation of charge-transfer-to-solvent (CTTS) states following X-ray absorption in aqueous solutions of Na+, Mg2+, and Al3+ ions. To explore the formation of such states in the aqueous phase, liquid-jet photoemission spectroscopy is employed. Using the core-hole-clock method, based on Auger-Meitner (AM) decay upon 1s excitation or ionization of the respective ions, upper limits are estimated for the metal-atom electron delocalization times to the neighboring water molecules. These delocalization processes represent the first steps in the formation of hydrated electrons, which are determined to take place on a timescale ranging from several hundred attoseconds (as) below the 1s ionization threshold to only 20 as far above the 1s ionization threshold. The decrease in the delocalization times as a function of the photon energy is continuous. This indicates that the excited electrons remain in the vicinity of the studied ions even above the ionization threshold, i.e., metal-ion electronic resonances associated with the CTTS state manifolds are formed. The three studied isoelectronic ions exhibit quantitative differences in their electron energetics and delocalization times, which are linked to the character of the respective excited states.

Center for Free Electron Laser Science DESY Notkestr 85 22607 Hamburg Germany

Department of Physical Chemistry University of Chemistry and Technology Prague Technická 5 166 28 Prague Czech Republic

Department of Physics and Astronomy Uppsala University Box 516 SE 751 20 Uppsala Sweden

Fritz Haber Institut der Max Planck Gesellschaft Faradayweg 4 6 14195 Berlin Germany

Institute for Electronic Structure Dynamics Helmholtz Zentrum Berlin für Materialien und Energie 14109 Berlin Germany

MAX 4 Laboratory Lund University Box 118 SE 22100 Lund Sweden

Synchrotron SOLEIL L'Orme des Merisiers Saint Aubin BP 48 91192 Gif sur Yvette Cedex Paris France

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