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

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 their fate in aqueous solution has remained a challenge. Here, we reveal the electronic dynamics induced by electronic relaxation through conical intersections in 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 find that such electronic dynamics are entirely suppressed when pyrazine is 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.

62 pages, 34 figures

References in corpus (5)

• Probing single-photon ionization on the attosecond time scale
• Catching Conical Intersections in the Act; Monitoring Transient Electronic Coherences by Attosecond Stimulated X-Ray Raman Signals
• eT 1.0: an open source electronic structure program with emphasis on coupled cluster and multilevel methods
• Decoherence and Revival in Attosecond Charge Migration Driven by Non-adiabatic Dynamics
• Mapping Electronic Decoherence Pathways in Molecules

Cited by in corpus (2)

• Decoherence dynamics in molecular qubits: Exponential, Gaussian and beyond
• Unifying Decoherence and Phase Evolution in Mixed Quantum-Classical Dynamics through Exact Factorization