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.
Bogot, A., Poline, M., Ji, M. et al. Unravelling non-adiabatic pathways in the mutual neutralization of hydronium and hydroxide.
Nat. Chem. 17, 541–546 (2025). https://doi.org/10.1038/s41557-025-01771-6
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Bogot, A., Poline, M., Ji, M. et al. Unravelling non-adiabatic pathways in the mutual neutralization of hydronium and hydroxide.
Nat. Chem. 17, 541–546 (2025). https://doi.org/10.1038/s41557-025-01771-6
Image Credits: AI Generated
DOI: https://doi.org/10.1038/s41557-025-01771-6
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Tags: D3O+ and OD− interactionselectron transfer mechanisms in reactionshydronium hydroxide reaction pathwaysintermediate unstable neutral D3O statekinetic isotope effect in chemistrymutual neutralization of hydronium and hydroxidenon-adiabatic chemical reactionsproduct channels in chemical reactionsradical formation in water microdropletsspontaneous formation of OH radicalsthree-body momentum correlationsthree-dimensional imaging in chemistry
