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

Conical intersections (CIs) dominate the pathways and outcomes of virtually all photophysical and photochemical molecular processes. Despite extensive experimental and theoretical effort, CIs have not been directly observed yet and the experimental evidence is being inferred from fast reaction rates...

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Bibliographic Details
Published in:Physical review letters 2015-11, Vol.115 (19), p.193003-193003, Article 193003
Main Authors: Kowalewski, Markus, Bennett, Kochise, Dorfman, Konstantin E, Mukamel, Shaul
Format: Article
Language:English
Subjects:
Coherence
Computer Simulation
Electronics
Femtosecond
Intersections
Models, Theoretical
Monitoring
Photochemical
Photochemical Processes
Photochemistry - methods
Spectral sensitivity
Spectrum Analysis, Raman - methods
X-rays
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Summary:Conical intersections (CIs) dominate the pathways and outcomes of virtually all photophysical and photochemical molecular processes. Despite extensive experimental and theoretical effort, CIs 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 CI with the adequate temporal and spectral sensitivity. The technique is based on a coherent Raman process that employs a composite femtosecond or attosecond x-ray pulse to detect the electronic coherences (rather than populations) that are generated as the system passes through the CI.
ISSN:0031-9007
1079-7114
DOI:10.1103/PhysRevLett.115.193003