Non-local analogues of Auger decay are increasingly recognized as important relaxation processes in the condensed phase. Here, we explore non-local autoionization, specifically Intermolecular Coulombic Decay (ICD), of a series of aqueous-phase isoelectronic cations following 1s core-level ionization. In particular, we focus on Na+, Mg2+, and Al3+ ions. We unambiguously identify the ICD contribution to the K-edge Auger spectrum. The different strength of the ion-water interactions is manifested by varying intensities of the respective signals: the ICD signal intensity is greatest for the Al3+ case, weaker for Mg2+, and absent for weakly-solvent-bound Na+. With the assistance of ab initio calculations and molecular dynamics simulations, we provide a microscopic understanding of the non-local decay processes. We assign the ICD signals to decay processes ending in two-hole states, delocalized between the central ion and neighbouring water. Importantly, these processes are shown to be highly selective with respect to the promoted water solvent ionization channels. Furthermore, using a core-hole-clock analysis, the associated ICD timescales are estimated to be around 76 fs for Mg2+ and 34 fs for Al3+. Building on these results, we argue that Auger and ICD spectroscopy represents a unique tool for the exploration of intra- and inter-molecular structure in the liquid phase, simultaneously providing both structural and electronic information.

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

Department of Chemistry and Industrial Chemistry University of Pisa Via Giuseppe Moruzzi 13 56124 Pisa Italy

Department of Locally Sensitive and Time Resolved Spectroscopy Helmholtz Zentrum Berlin für Materialien und Energie 14109 Berlin Germany

Department of Physical Chemistry University of Chemistry and Technology Technická 5 Prague 6 166 28 Czech Republic

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

Institut für Kernphysik Goethe Universität Frankfurt am Main Max von Laue Straße 1 60438 Frankfurt am Main Germany

MAX 4 Laboratory Lund University Box 118 SE 22100 Lund Sweden

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

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

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