Visualizing Conical Intersection Passages via Vibronic Coherence Maps Generated by Stimulated Ultrafast X--Ray Raman Signals

Abstract

The rates and outcomes of virtually all photophysical and photochemical processes are determined by Conical Intersections. These are regions of degeneracy between electronic states on the nuclear landscape of molecules where electrons and nuclei evolve on comparable timescales and become strongly coupled, enabling radiationless relaxation channels upon optical excitation. Due to their ultrafast nature and vast complexity, monitoring Conical Intersections experimentally is an open challenge. We present a simulation study on the ultrafast photorelaxation of uracil, which demonstrates a new window into Conical Intersections obtained by recording the transient wavepacket coherence during this passage with an x-ray free electron laser pulse. We report two major findings. First, we find that the vibronic coherence at the conical intersection lives for several hundred femtoseconds and can be measured during this entire time. Second, the time-dependent energy splitting landscape of the participating vibrational and electronic states is directly extracted from Wigner spectrograms of the signal. These offer a novel physical picture of the quantum Conical Intersection pathways through visualizing their transient vibronic coherence distributions. The path of a nuclear wavepacket around the Conical Intersection is directly mapped by the proposed experiment.

7 pages, 5 Figures, to be published in PNAS

References in corpus (3)

• Imaging the Photochemical Ring-Opening of 1,3-Cyclohexadiene by Ultrafast Electron Diffraction
• Tracking Attosecond Electronic Coherences Using Phase-Manipulated Extreme Ultraviolet Pulses
• Towards attochemistry: Control of nuclear motion through conical intersections and electronic coherences

Cited by in corpus (4)

• Decoherence and Revival in Attosecond Charge Migration Driven by Non-adiabatic Dynamics
• Electronic Quantum Coherence in Glycine Molecules Probed with Ultrashort X-ray Pulses in Real Time
• Probing Nonadiabatic Dynamics with Attosecond Pulse Trains and Soft X-ray Raman Spectroscopy
• Capturing Fingerprints of Conical Intersection: Complementary Information of Non-Adiabatic Dynamics from Linear X-ray Probes