Observation of an Associative State in Aqueous Hydroxide
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.
Authors
- Michael Odelius (ORCID: https://orcid.org/0000-0002-7023-2486)
- Yi‐Tao Cui (ORCID: https://orcid.org/0000-0001-7104-0059)
- Victor Kimberg (ORCID: https://orcid.org/0000-0003-1269-8760)
- Zhong Yin (ORCID: https://orcid.org/0000-0001-5594-9879)
- Stephan Thürmer (ORCID: https://orcid.org/0000-0002-8146-4573)
- Hans Jakob Wörner
- Evanthia Chatzigeorgiou (ORCID: https://orcid.org/0000-0001-5183-8020)
- Sergey P. Polyutov (ORCID: https://orcid.org/0000-0003-1366-1986)
- Павел О. Краснов (ORCID: https://orcid.org/0000-0002-5843-0455)
- Takashi Tokushima (ORCID: https://orcid.org/0000-0003-2586-0712)
- Yoshihisa Harada (ORCID: https://orcid.org/0000-0002-4590-9109)
- Kosuke Yamazoe (ORCID: https://orcid.org/0000-0002-7249-7090)
- Johan Gråsjö (ORCID: https://orcid.org/0000-0002-0080-3714)
- Conny Såthe (ORCID: https://orcid.org/0000-0001-7799-8575)
- Jun Miyawaki (ORCID: https://orcid.org/0000-0002-0602-907X)
- Jan‐Erik Rubensson (ORCID: https://orcid.org/0000-0003-1467-8114)
- Faris Gel’mukhanov (ORCID: https://orcid.org/0000-0002-8272-7670)
Institutions
- Uppsala University (SE)
- Stockholm University (SE)
- Lund University (SE)
- Tohoku University (JP)
- Kyoto University (JP)
- ETH Zurich (CH)
- Institute for Solid State Physics and Optics (HU)
- MAX IV Laboratory (SE)
- Siberian Federal University (RU)
- The University of Tokyo (JP)
- KTH Royal Institute of Technology (SE)
- Graduate School USA (US)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-03-11
- DOI
- https://doi.org/10.1021/jacs.4c13453
- Citations
- 1
- Primary Topic
- Spectroscopy and Quantum Chemical Studies
- Type
- article
- Field-Weighted Citation Impact
- 1.25
Funders
- Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung
- Eidgenössische Technische Hochschule Zürich
- Vetenskapsrådet
- Ministry of Science and Higher Education of the Russian Federation
- Japan Society for the Promotion of Science