These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
Ultrafast Relaxation Dynamics of the S1 (nπ*) State and the 3p and 3d Rydberg States in Cyclohexanone by Femtosecond Photoelectron Imaging
preprintsubmitted 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.