Ultrafast X-ray spectroscopy of conical intersections

Abstract

Ongoing developments in ultrafast X-ray sources offer powerful new means of probing the com- plex non-adiabatically coupled structural and electronic dynamics of photoexcited molecules. These non-Born-Oppenheimer effects are governed by general electronic degeneracies termed conical in- tersections which play a key role, analogous to that of a transition state, in the electronic-nuclear dynamics of excited molecules. Using high level ab initio quantum dynamics simulations, we studied time-resolved X-ray absorption and photoelectron spectroscopy (TRXAS and TRXPS, respectively) of the prototypical unsaturated organic chromophore, ethylene, following excitation to its S2 state. The TRXAS in particular is highly sensitive to all aspects of the ensuing dynamics. These X-ray spectroscopies provide a clear signature of the wavepacket dynamics near conical intersections, related to charge localization effects driven by the nuclear dynamics. Given the ubiquity of charge localization in excited state dynamics, we believe that ultrafast X-ray spectroscopies offer a unique and powerful route to the direct observation of dynamics around conical intersections.

5 pages, 4 figures

References in corpus (3)

• Catching Conical Intersections in the Act; Monitoring Transient Electronic Coherences by Attosecond Stimulated X-Ray Raman Signals
• Ultrafast Internal Conversion in Ethylene I. The Excited State Lifetime
• Ultrafast Internal Conversion in Ethylene. II. Mechanisms and Pathways for Quenching and Hydrogen Elimination

Cited by in corpus (20)

• Tunable Isolated Attosecond X-ray Pulses with Gigawatt Peak Power from a Free-Electron Laser
• Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy
• Visualizing Conical Intersection Passages via Vibronic Coherence Maps Generated by Stimulated Ultrafast X--Ray Raman Signals
• The quest to simulate excited-state dynamics of transition metal complexes
• An Assessment of Different Electronic Structure Approaches for Modeling Time-Resolved X-ray Absorption Spectroscopy
• Non-Adiabatic Electronic and Vibrational Ring-Opening Dynamics resolved with Attosecond Core-Level Spectroscopy
• Transient Resonant Auger-Meitner Spectra of Photoexcited Thymine
• Theory of x-ray scattering from laser-driven electronic systems
• Prediction challenge: First principles simulation of the ultrafast electron diffraction spectrum of cyclobutanone
• Probing Nonadiabatic Dynamics with Attosecond Pulse Trains and Soft X-ray Raman Spectroscopy
• Generalization of one-center non orthogonal configuration interaction singles to open shell singlet reference states: Theory and application to valence-core pump-probe states in acetylacetone
• Ultrafast Charge Migration Dynamics in Enol Keto Tautomerization Monitored with a Local Soft-X-Ray Probe
• Capturing Fingerprints of Conical Intersection: Complementary Information of Non-Adiabatic Dynamics from Linear X-ray Probes
• Resolving Competing Conical Intersection Pathways: Time-Resolved X-ray Absorption Spectroscopy of trans-1,3-Butadiene
• A Laboratory Frame Density Matrix for Ultrafast Quantum Molecular Dynamics
• Controlling energy conservation in quantum dynamics with independently moving basis functions: Application to Multi-Configuration Ehrenfest
• Retrieving genuine nonlinear Raman responses in ultrafast spectroscopy via deep learning
• Exponential convergence of the local diabatic representation for nonadiabatic models
• Element- and enantiomer-selective visualization of ibuprofen dimer vibrations
• Photoinduced enhancement of chemical shift sensitivity to local vibrations