Catching Conical Intersections in the Act; Monitoring Transient Electronic Coherences by Attosecond Stimulated X-Ray Raman Signals

Abstract

Conical intersections (CoIn) dominate the pathways and outcomes of virtually all photophysical and photochemical molecular processes. Despite extensive experimental and theoretical effort, CoIns have not been directly observed yet and the experimental evidence is being inferred from fast reaction rates and some vibrational signatures. We show that short X-ray (rather than optical) pulses can directly detect the passage through a CoIn with the adequate temporal and spectral sensitivity. The technique is based on a coherent Raman process that employs a composite femtosecond/attosecond X-ray pulse to detect the electronic coherences (rather than populations) that are generated as the system passes through the CoIn.

References in corpus (4)

• Bright Coherent Ultrahigh Harmonics in the keV X-Ray Regime from Mid-Infrared Femtosecond Lasers
• Coherent Raman spectro-imaging with laser frequency combs
• Detecting Electronic Coherence by Multidimensional Broadband Stimulated X-Ray Raman Signals
• Transient Impulsive Giant Electronic Raman Redistribution

Cited by in corpus (29)

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• Decoherence and Revival in Attosecond Charge Migration Driven by Non-adiabatic Dynamics
• Towards attochemistry: Control of nuclear motion through conical intersections and electronic coherences
• Visualizing Conical Intersection Passages via Vibronic Coherence Maps Generated by Stimulated Ultrafast X--Ray Raman Signals
• Monitoring Nonadiabatic Avoided Crossing Dynamics in Molecules by Ultrafast X-Ray Diffraction
• The quest to simulate excited-state dynamics of transition metal complexes
• Atomic, molecular and optical physics applications of longitudinally coherent and narrow bandwidth Free-Electron Lasers
• Monitoring Nonadiabatic Electron-Nuclear Dynamics in Molecules by Attosecond Streaking of Photoelectrons
• Electronic Quantum Coherence in Glycine Molecules Probed with Ultrashort X-ray Pulses in Real Time
• Exploring the many-body dynamics near a conical intersection with trapped Rydberg ions
• Accessing Excited State Molecular Vibrations by Femtosecond Stimulated Raman Spectroscopy
• Electronic dynamics created at conical intersections and its dephasing in aqueous solution
• Simulating conical intersection dynamics in the condensed phase with hybrid quantum master equations
• Ultrafast x-ray-induced nuclear dynamics in diatomic molecules using femtosecond x-ray/x-ray pump-probe spectroscopy
• Search for long lasting electronic coherence using on-the-fly ab initio semiclassical dynamics
• High temporal and spectral resolution of stimulated x-ray Raman signals with stochastic free-electron-laser pulses
• Coupled nuclear and electron dynamics in the vicinity of a conical intersection
• Local diabatic representation of conical intersection quantum dynamics
• Probing Nonadiabatic Dynamics with Attosecond Pulse Trains and Soft X-ray Raman Spectroscopy
• Ultrafast Molecular Frame Quantum Tomography
• Multistate metadynamics for automatic exploration of conical intersections
• Capturing Fingerprints of Conical Intersection: Complementary Information of Non-Adiabatic Dynamics from Linear X-ray Probes
• A Laboratory Frame Density Matrix for Ultrafast Quantum Molecular Dynamics
• Coherent control using kinetic energy and the geometric phase of a conical intersection
• Stimulated Raman lineshapes in the large light-matter interaction limit
• Simulating Nonadiabatic Dynamics in Benzophenone: Tracing Internal Conversion Through Photoelectron Spectra
• Variational Density Functional Calculations of Excited States: Conical Intersection and Avoided Crossing in Ethylene Bond Twisting