Despite decades of research, our understanding of radiation damage in aqueous systems remains limited. The recent discovery of Intermolecular Coulombic Decay (ICD) following inner-valence ionization of liquid water raises interesting questions about its efficiency as a major source of low-energy electrons responsible for radiation damage. To investigate, we performed electron-electron coincidence measurements on liquid H2O and D2O using a monochromatized high-harmonic-generation light source, detecting ICD electrons in coincidence with photoelectrons from the 2a1 shell. We find that the ICD efficiency γ is below unity in both liquids and that γ(H2O)/γ(D2O) = 0.86 ± 0.03. Ab initio calculations reveal that ICD competes with proton transfer and non-adiabatic relaxation, which can close the ICD channel. A multi-scale stochastic model incorporating solvent effects reproduces these efficiencies. Our combined experimental and theoretical results suggest that the higher ICD efficiency in D2O arises from slower proton transfer and non-adiabatic transitions, highlighting the crucial role of nuclear motion in liquid-phase ICD and advancing the understanding of radiation damage.

Beijing National Laboratory for Condensed Matter Physics and Institute of Physics Chinese Academy of Sciences Beijing China

Charles University Faculty of Mathematics and Physics Institute of Theoretical Physics Prague Czech Republic

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

Laboratory of Physical Chemistry ETH Zürich Zurich Switzerland

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