Targeting individual tautomers in equilibrium by resonant inelastic X-ray scattering
- Tautomerism is one of the most important forms of isomerism, owing to the facile interconversion between species and the large differences in chemical properties introduced by the proton transfer connecting the tautomers. Spectroscopic techniques are often used for the characterization of tautomers. In this context, separating the overlapping spectral response of coexisting tautomers is a long-standing challenge in chemistry. Here, we demonstrate that by using resonant inelastic X-ray scattering tuned to the core excited states at the site of proton exchange between tautomers one is able to experimentally disentangle the manifold of valence excited states of each tautomer in a mixture. The technique is applied to the prototypical keto-enol equilibrium of 3-hydroxypyridine in aqueous solution. We detect transitions from the occupied orbitals into the LUMO for each tautomer in solution, which report on intrinsic and hydrogen-bond-induced orbital polarization within the pi and sigma manifolds at the proton-transfer site.
Author details: | Vinicius Vaz da CruzORCiD, Robby BüchnerORCiDGND, Mattis FondellORCiD, Annette PietzschORCiD, Sebastian EckertORCiDGND, Alexander FöhlischORCiDGND |
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DOI: | https://doi.org/10.1021/acs.jpclett.1c03453 |
ISSN: | 1948-7185 |
Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/35266716 |
Title of parent work (English): | The journal of physical chemistry letters |
Publisher: | American Chemical Society |
Place of publishing: | Washington |
Publication type: | Article |
Language: | English |
Date of first publication: | 2022/03/17 |
Publication year: | 2022 |
Release date: | 2024/01/03 |
Tag: | Equilibrium; Molecular structure; Molecules; Nitrogen; Solvents |
Volume: | 13 |
Issue: | 10 |
Number of pages: | 8 |
First page: | 2459 |
Last Page: | 2466 |
Funding institution: | ERC-ADG-2014 Advanced Investigator Grant under the Horizon 2020 EU; Framework, Programme for Research and Innovation [669531 EDAX] |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Physik und Astronomie |
DDC classification: | 5 Naturwissenschaften und Mathematik / 53 Physik / 530 Physik |
Peer review: | Referiert |
Publishing method: | Open Access / Hybrid Open-Access |
License (German): | CC-BY-NC-ND - Namensnennung, nicht kommerziell, keine Bearbeitungen 4.0 International |