Electronic dynamics created at conical intersections and its dephasing in aqueous solution
A dynamical rearrangement in the electronic structure of a molecule can be driven by different phenomena, including nuclear motion, electronic coherence or electron correlation. Recording such electronic dynamics and identifying its fate in an aqueous solution has remained a challenge. Here, we reveal the electronic dynamics induced by electronic relaxation through conical intersections in both isolated and solvated pyrazine molecules using X-ray spectroscopy. We show that the ensuing created dynamics corresponds to a cyclic rearrangement of the electronic structure around the aromatic ring. Furthermore, we found that such electronic dynamics were entirely suppressed when pyrazine was dissolved in water. Our observations confirm that conical intersections can create electronic dynamics that are not directly excited by the pump pulse and that aqueous solvation can dephase them in less than 40 fs. These results have implications for the investigation of electronic dynamics created during light-induced molecular dynamics and shed light on their susceptibility to aqueous solvation.
Authors
- Yi–Ping Chang (ORCID: https://orcid.org/0000-0002-2967-8910)
- Hans Jakob Wörner (ORCID: https://orcid.org/0000-0002-8877-0872)
- Zhong Yin (ORCID: https://orcid.org/0000-0001-5594-9879)
- Jean‐Pierre Wolf (ORCID: https://orcid.org/0000-0003-3729-958X)
- Tadas Balčiūnas (ORCID: https://orcid.org/0000-0001-7713-3344)
- Alexander C. Paul (ORCID: https://orcid.org/0000-0002-7547-445X)
- Henrik Koch (ORCID: https://orcid.org/0000-0002-8367-8727)
- Bruno Nunes Cabral Tenorio (ORCID: https://orcid.org/0000-0002-9702-998X)
- Marin Sapunar (ORCID: https://orcid.org/0000-0002-5717-1930)
- Sonia Coriani (ORCID: https://orcid.org/0000-0002-4487-897X)
- Shota Tsuru (ORCID: https://orcid.org/0000-0003-0014-7873)
Institutions
- Madrid Institute for Advanced Studies (ES)
- University of Geneva (CH)
- Tohoku University (JP)
- Norwegian University of Science and Technology (NO)
- ETH Zurich (CH)
- Ruđer Bošković Institute (HR)
- RIKEN Center for Computational Science (JP)
- Ruhr University Bochum (DE)
- European X-Ray Free-Electron Laser (DE)
- Technical University of Denmark (DK)
Publication Details
- Journal
- Nature Physics
- Published
- 2024-11-27
- DOI
- https://doi.org/10.1038/s41567-024-02703-w
- Citations
- 21
- Primary Topic
- Spectroscopy and Quantum Chemical Studies
- Type
- article
- Field-Weighted Citation Impact
- 7.09
Funders
- National Science Foundation
- Alexander von Humboldt-Stiftung
- European Commission
- Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung
- Eidgenössische Technische Hochschule Zürich
- Hrvatska Zaklada za Znanost
- Danish e-Infrastructure Cooperation
- Norges Forskningsråd
- Ruhr-Universität Bochum