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<p>The mutual neutralization of hydronium and hydroxide ions is a fundamental chemical reaction. Yet, there is very limited direct experimental evidence about its intrinsically non-adiabatic mechanism. Chemistry textbooks describe the products of mutual neutralization in bulk water as two water molecules; however, this reaction has been suggested as a possible mechanism for the recently reported spontaneous formation of OH radicals at the surface of water microdroplets. Here, following three-dimensional-imaging of the coincident neutral products of reactions of isolated D<sub>3</sub>O<sup>+</sup> and OD<sup>−</sup>, we can reveal the non-adiabatic pathways for OD radical formation. Two competing pathways lead to distinct D<sub>2</sub>O + OD + D and 2OD + D<sub>2</sub> product channels, while the proton-transfer mechanism is substantially suppressed due to a kinetic isotope effect. Analysis of the three-body momentum correlations revealed that the D<sub>2</sub>O + OD + D channel is formed by electron transfer at a short distance of ~4 Å with the formation of the intermediate unstable neutral D<sub>3</sub>O ground state, while 2OD + D<sub>2</sub> products are obtained following electron transfer at a distance of ~10 Å via an excited state of the neutral D<sub>3</sub>O.</p><p></p>

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Unravelling non-adiabatic pathways in the mutual neutralization of hydronium and hydroxide

  • 期刊论文

  • 发表日期：

    2025年3月25日

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  • Alon Bogot,
  • Mathias Poline,
  • MingChao Ji,
  • Arnaud Dochain,
  • Stefan Rosén,
  • Henning Zettergren,
  • Henning T. Schmidt,
  • Richard D. Thomas,
  • Daniel Strasser

摘要

The mutual neutralization of hydronium and hydroxide ions is a fundamental chemical reaction. Yet, there is very limited direct experimental evidence about its intrinsically non-adiabatic mechanism. Chemistry textbooks describe the products of mutual neutralization in bulk water as two water molecules; however, this reaction has been suggested as a possible mechanism for the recently reported spontaneous formation of OH radicals at the surface of water microdroplets. Here, following three-dimensional-imaging of the coincident neutral products of reactions of isolated D3O+ and OD−, we can reveal the non-adiabatic pathways for OD radical formation. Two competing pathways lead to distinct D2O + OD + D and 2OD + D2 product channels, while the proton-transfer mechanism is substantially suppressed due to a kinetic isotope effect. Analysis of the three-body momentum correlations revealed that the D2O + OD + D channel is formed by electron transfer at a short distance of ~4 Å with the formation of the intermediate unstable neutral D3O ground state, while 2OD + D2 products are obtained following electron transfer at a distance of ~10 Å via an excited state of the neutral D3O.