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Observation of an Associative State in Aqueous Hydroxide
Tohoku Univ, Int Ctr Synchrotron Radiat Innovat Smart, Sendai 9808572, Japan.;Swiss Fed Inst Technol, Lab Phys Chem, CH-8093 Zurich, Switzerland..ORCID iD: 0000-0001-5594-9879
Siberian Fed Univ, Int Res Ctr Spect & Quantum Chem, Krasnoyarsk 660041, Russia..ORCID iD: 0000-0002-5843-0455
Kyoto Univ, Grad Sch Sci, Dept Chem, Kyoto 6068502, Japan..ORCID iD: 0000-0002-8146-4573
Uppsala Univ, Dept Phys & Astron, S-75120 Uppsala, Sweden..
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2025 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 147, no 11, p. 9190-9197Article in journal (Refereed) Published
Abstract [en]

The dynamics of chemical reactions in solution are of paramount importance in fields ranging from biology to materials science. Because the hydrogen-bond network and proton dynamics govern the behavior of aqueous solutions, they have been the subject of numerous studies over the years. Here, we report the observation of a previously unknown associative state in the hydroxide ion that forms when a proton from a neighboring water molecule approaches the hydroxide ion, utilizing resonant inelastic soft X-ray scattering (RIXS) and quantum dynamical simulations. State-of-the-art theoretical analysis reveals state mixing in the electronically excited states between aqueous hydroxide ions and the solvent. Our results give new insights into chemical bonding and excited-state dynamics in the aqueous environment. This investigation of associative states opens up new pathways for spectroscopic studies of chemical reaction dynamics and lays the foundation for directly accessing dynamic proton exchange in solution.

Place, publisher, year, edition, pages
American Chemical Society (ACS) , 2025. Vol. 147, no 11, p. 9190-9197
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-361556DOI: 10.1021/jacs.4c13453ISI: 001442042400001PubMedID: 40064888Scopus ID: 2-s2.0-86000490829OAI: oai:DiVA.org:kth-361556DiVA, id: diva2:1946884
Note

QC 20250324

Available from: 2025-03-24 Created: 2025-03-24 Last updated: 2025-03-24Bibliographically approved

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Gel'mukhanov, FarisKimberg, Victor

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