Intermolecular Coulombic decay (ICD) is a ubiquitous relaxation channel of electronically excited states in weakly bound systems, ranging from dimers to liquids. As it is driven by electron correlation, it was assumed that it will dominate over more established energy loss mechanisms, for example fluorescence. Here, we use electron-electron coincidence spectroscopy to determine the efficiency of the ICD process after 2a1 ionization in water clusters. We show that this efficiency is surprisingly low for small water clusters and that it gradually increases to 40-50% for clusters with hundreds of water units. Ab initio molecular dynamics simulations reveal that proton transfer between neighboring water molecules proceeds on the same timescale as ICD and leads to a configuration in which the ICD channel is closed. This conclusion is further supported by experimental results from deuterated water. Combining experiment and theory, we infer an intrinsic ICD lifetime of 12-52 fs for small water clusters.

Department of Physical Chemistry University of Chemistry and Technology Prague Technická 5 16628 Prague 6 Czech Republic

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

Institute for Optics and Atomic Physics Technical University Berlin Hardenbergstr 36 10623 Berlin Germany

Laboratoire de Chimie Physique Matière et Rayonnement UMR 7614 Sorbonne Université CNRS F 75005 Paris France

Leibniz Institute of Surface Engineering Permoserstr 15 04318 Leipzig Germany

Max Planck Institute for Plasma Physics Boltzmannstr 2 85748 Garching Germany

Max Planck Institute for Plasma Physics Wendelsteinstr 1 17491 Greifswald Germany

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