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.

Publication Details

Journal
Repository for Publications and Research Data (ETH Zurich)
Published
2025-01-01
DOI
https://doi.org/10.3929/ethz-b-000707974
Primary Topic
Spectroscopy and Quantum Chemical Studies
Type
article
Field-Weighted Citation Impact
0.00
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article

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

Repository for Publications and Research Data (ETH Zurich)
Spectroscopy and Quantum Chemical Studies
article

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

article en

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.

Repository for Publications and Research Data (ETH Zurich)
Clean water and sanitation
Openalex Percentile: Top 56%
Spectroscopy and Quantum Chemical Studies
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Electronic dynamics created at conical intersections and its dephasing in aqueous solution · Repository for Publications and Research Data (ETH Zurich) (2025) | TGRS Research Map | TGRS