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Ultrafast Relaxation Dynamics of the S1 (nπ*) State and the 3p and 3d Rydberg States in Cyclohexanone by Femtosecond Photoelectron Imaging

preprint
submitted on 12.03.2019, 16:27 and posted on 13.03.2019, 13:16 by Ole Hüter, Niklas Helle, Friedrich Temps
The radiationless decay dynamics of the S1 (nπ*) state and the 3p and 3d Rydberg states of cyclohexanone are investigated using femtosecond time-resolved time-of- flight mass spectrometry and photoelectron imaging spectroscopy. After two-photon excitation of the 3p and 3d states, an ultrafast population transfer to the 3s state is observed within < 120 fs. We ascribe this behavior to strong vibronic interactions of the excited Rydberg states with the 1ππ* valence state that enable an ultrafast population transfer via an avoided crossing and the subsequent passage of a conical intersection between the respective electronic states. Eventually, the 3s state deactivates by internal conversion to the S1 (nπ*) state, which in turn is found to be long-lived with a decay time of ~ 300 - 800 ps.

Funding

Deutsche Forschungsgemeinschaft

History

Email Address of Submitting Author

temps@phc.uni-kiel.de

Institution

Institute of Physical Chemistry, Christian-Albrechts-University Kiel

Country

Germany

ORCID For Submitting Author

0000-0002-8395-7275

Declaration of Conflict of Interest

No conflict of interest

Version Notes

Version 1.0

Exports