Direct observation of ultrafast symmetry reduction during internal conversion of 2-thiouracil using Coulomb explosion imaging
The photochemistry of heterocyclic molecules plays a decisive role for processes and applications like DNA photo-protection from UV damage and organic photocatalysis. The photochemical reactivity of heterocycles is determined by the redistribution of photoenergy into electronic and nuclear degrees of freedom, initially involving ultrafast internal conversion. Most heterocycles are planar in their ground state and internal conversion requires symmetry breaking. To lower the symmetry, the molecule must undergo an out-of-plane motion, which has not yet been observed directly. Here we show using the example of 2-thiouracil, how Coulomb explosion imaging can be utilized to extract comprehensive information on this molecular deformation, linking the extracted deplanarization of the molecular geometry to the previously studied temporal evolution of its electronic properties. Particularly, the protons of the exploded molecule are well-suited messengers carrying rich information on its geometry at distinct times after electronic excitation. We expect that our new analysis approach centered on these peripheral protons can be adapted as a general concept for future time-resolved studies of complex molecules in the gas phase.
Authors
- T. Jahnke (ORCID: https://orcid.org/0000-0003-1358-5629)
- Gregor Kastirke
- Daniel Rolles (ORCID: https://orcid.org/0000-0002-3965-3477)
- Markus Gühr
- A. Atia-Tul-Noor
- Anbu Selvam Venkatachalam (ORCID: https://orcid.org/0000-0002-5206-6955)
- Surjendu Bhattacharyya (ORCID: https://orcid.org/0000-0001-7107-8006)
- Markus Ilchen (ORCID: https://orcid.org/0000-0001-5201-0495)
- Terry Mullins (ORCID: https://orcid.org/0000-0002-9358-3158)
- Sebastian Mai (ORCID: https://orcid.org/0000-0001-5327-8880)
- Heide Ibrahim (ORCID: https://orcid.org/0000-0001-6371-8501)
- Yevheniy Ovcharenko (ORCID: https://orcid.org/0000-0001-6804-9781)
- Fabiano Lever (ORCID: https://orcid.org/0000-0002-8448-7594)
- Björn Senfftleben (ORCID: https://orcid.org/0000-0003-1716-5445)
- Sergey Usenko (ORCID: https://orcid.org/0000-0001-5202-5267)
- Keyu Chen (ORCID: https://orcid.org/0000-0001-6692-1089)
- Artem Rudenko (ORCID: https://orcid.org/0000-0002-9154-8463)
- Ulrike Frühling (ORCID: https://orcid.org/0000-0002-8423-786X)
- Alice E. Green (ORCID: https://orcid.org/0000-0002-6897-1247)
- Rebecca A. Ingle (ORCID: https://orcid.org/0000-0002-0566-3407)
- Florian Trinter (ORCID: https://orcid.org/0000-0002-0891-9180)
- Simon Dold (ORCID: https://orcid.org/0000-0001-5332-8251)
- Huynh Van Sa Lam (ORCID: https://orcid.org/0000-0003-4767-5390)
- Dennis Mayer (ORCID: https://orcid.org/0000-0002-1858-6818)
- Rebecca Boll (ORCID: https://orcid.org/0000-0001-6286-4064)
- Michael Meyer (ORCID: https://orcid.org/0000-0002-1444-6770)
- Maria Elena Castellani
- Tommaso Mazza (ORCID: https://orcid.org/0000-0003-3105-459X)
Institutions
- Goethe University Frankfurt (DE)
- University of Vienna (AT)
- University of Ottawa (CA)
- Universität Hamburg (DE)
- Kansas State University (US)
- Fritz Haber Institute of the Max Planck Society (DE)
- Deutsches Elektronen-Synchrotron DESY (DE)
- SLAC National Accelerator Laboratory (US)
- Institut National de la Recherche Scientifique (CA)
- Azienda USL di Bologna (IT)
- Hamburg Institut (Germany) (DE)
- Max Planck Institute for Nuclear Physics (DE)
- University College London (GB)
- European X-Ray Free-Electron Laser (DE)
Publication Details
- Journal
- Nature Communications
- Published
- 2025-02-28
- DOI
- https://doi.org/10.1038/s41467-025-57083-3
- Citations
- 11
- Primary Topic
- Laser-Matter Interactions and Applications
- Type
- article
- Field-Weighted Citation Impact
- 13.71
Funders
- National Science Foundation
- Deutsche Forschungsgemeinschaft
- Austrian Science Fund
- Natural Sciences and Engineering Research Council of Canada
- Chemical Sciences, Geosciences, and Biosciences Division