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Electron dynamics in water are of fundamental importance for a broad range of phenomena1-3, but their real-time study faces numerous conceptual and methodological challenges4-6. Here, we introduce attosecond size-resolved cluster spectroscopy and build up a molecular-level understanding of the attosecond electron dynamics in water. We measure the effect that the addition of single water molecules has on the photoionization time delays7-9 of water clusters. We find a continuous increase of the delay for clusters containing up to 4-5 molecules and little change towards larger clusters. We show that these delays are proportional to the spatial extension of the created electron hole, which first increases with cluster size and then partially localizes through the onset of structural disorder that is characteristic of large clusters and bulk liquid water. These results suggest a previously unknown sensitivity of photoionization delays to electron-hole delocalization and indicate a direct link between electronic structure and attosecond photoionization dynamics. Our results offer novel perspectives for studying electron/hole delocalization and its attosecond dynamics.

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