Investigation of Complex Relaxation Dynamics of Nearly Degenerated Rydberg States in Acetone

<div>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 <sup>1</sup>ππ* 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 S<sub>1</sub> (nπ*) state, which in turn is found to be long-lived with a decay time of ~ 300 - 800 ps.</div>

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Electronic and vibrational relaxation dynamics of NH3 Rydberg states probed by vacuum-ultraviolet time-resolved photoelectron imaging

The Journal of Chemical Physics ◽

10.1063/1.5116707 ◽

2019 ◽

Vol 151 (10) ◽

pp. 104306 ◽

Cited By ~ 2

Author(s):

Vít Svoboda ◽

Chuncheng Wang ◽

Max D. J. Waters ◽

Hans Jakob Wörner

Keyword(s):

Vibrational Relaxation ◽

Vacuum Ultraviolet ◽

Rydberg States ◽

Relaxation Dynamics ◽

Photoelectron Imaging ◽

Time Resolved

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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

10.26434/chemrxiv.7832177 ◽

2019 ◽

Author(s):

Ole Hüter ◽

Niklas Helle ◽

Friedrich Temps

Keyword(s):

Imaging Spectroscopy ◽

Rydberg States ◽

Population Transfer ◽

Relaxation Dynamics ◽

Photoelectron Imaging ◽

Time Resolved ◽

Flight Mass Spectrometry ◽

Vibronic Interactions ◽

Photon Excitation ◽

Photoelectron Imaging Spectroscopy

<div>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 <sup>1</sup>ππ* 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 S<sub>1</sub> (nπ*) state, which in turn is found to be long-lived with a decay time of ~ 300 - 800 ps.</div>

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