Unconventional atomic-level mechanism induced by a submerged saddle in the O(1D) + CH3OCH3 reaction
reaction, we demonstrate that the accepted insertion mechanisms, including O-insertion into C-O bonds, do not occur, and reveal an unconventional atomic-level mechanism, designated as O+H-C collision activation stereocyclization, that supersedes O-insertion into C-H bonds. Dynamics calculations, performed on a high-level ab initio potential energy surface, yield rate coefficients in very good agreement with experiment, exhibiting an unexpected increase with temperature. This finding is attributed to an unusual submerged saddle as part of the unconventional mechanism. As this mechanism probably exists in other excited-state atom reactions, the dynamical effects uncovered here are expected to have general significance.
Authors
- Kevin M. Hickson (ORCID: https://orcid.org/0000-0001-8317-2606)
- Wensheng Bian (ORCID: https://orcid.org/0000-0003-2125-8054)
- Jianwei Cao
- Jintao Xie
- Xingyu Yang
- Fengyi Li
Institutions
- Centre National de la Recherche Scientifique (FR)
- Université de Bordeaux (FR)
- Chinese Academy of Sciences (CN)
- Institut des Sciences Moléculaires (FR)
- Beijing National Laboratory for Molecular Sciences (CN)
- Institute of Chemistry (CN)
- Institut Polytechnique de Bordeaux (FR)
- University of Chinese Academy of Sciences (CN)
Publication Details
- Journal
- Communications Chemistry
- Published
- 2026-04-16
- DOI
- https://doi.org/10.1038/s42004-026-02018-2
- Primary Topic
- Advanced Chemical Physics Studies
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Natural Science Foundation of China
- Centre National d’Etudes Spatiales
- Centre National de la Recherche Scientifique
- Institute of Chemistry, Chinese Academy of Sciences