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<p>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&#xa0;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 H<sub>2</sub>O and D<sub>2</sub>O using a monochromatized high-harmonic-generation light source, detecting ICD electrons in coincidence with photoelectrons from the 2a<sub>1</sub> shell. We find that the&#xa0;ICD efficiency γ is below unity in both liquids and that γ(H<sub>2</sub>O)/γ(D<sub>2</sub>O) = 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 D<sub>2</sub>O 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.</p>

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Intermolecular Coulombic decay in liquid water competes with proton transfer and non-adiabatic relaxation

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年7月22日

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  • Pengju Zhang,
  • Joel Trester,
  • Jakub Dubský,
  • Přemysl Kolorenč,
  • Petr Slavíček,
  • Hans Jakob Wörner

摘要

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.