Electronic dynamics created at conical intersections and its dephasing in aqueous solution

Chang, Yi-Ping; Balciunas, Tadas; Yin, Zhong; Sapunar, Marin; Tenorio, Bruno N. C.; Paul, Alexander C.; Tsuru, Shota; Koch, Henrik; Wolf, Jean-Pierre; Coriani, Sonia; Wörner, Hans Jakob (2025) Electronic dynamics created at conical intersections and its dephasing in aqueous solution. Nature Physics, 21 (1). pp. 137-145. ISSN 1745-2473

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Official URL: http://doi.org/10.1038/s41567-024-02703-w

Abstract

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.

Item Type:

Article

Uncontrolled Keywords:

electronic structure of atoms and molecules ; atomic and molecular interactions with photons; spectroscopy; coherence; phase; pulse

Subjects:

NATURAL SCIENCES > Chemistry
NATURAL SCIENCES > Chemistry > Physical Chemistry

Divisions:

Division of Physical Chemistry

Projects: