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Updated: Mar 3, 2026

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
Superexcited State Dynamics of OCS: An Experimental Identification of Three Competing Decay Channels among
Qiaoli Hao1,2, Jinyou Long1,2, Xulan Deng1,2
1State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences , Wuhan 430071, PR China.
Abstract:
The 7sσ and 6pσ superexcited Rydberg states of OCS belonging to series converging onto the B̃2Σ+ ionic limit have been successfully prepared by three-photon UV excitation, and their ensuing competing relaxation processes have been probed by a time-delayed IR ionization pulse. The time profiles of S+ ions, which encode their fragmentation mechanism, are only observable at high pump intensities, thus providing unique experimental identification of the neutral predissociation channel producing S* atoms. Benefiting from this feature and by comparison with the time behavior of OCS+ ions, three competing relaxation channels are identified: autoionization associated with both X̃2Π and Ã2Π ionic states; internal conversion to isoenergetic RA states, the deactivation of which manifests as a picosecond decay in the time profile of OCS+ ions; picosecond neutral predissociation appearing as a nondecaying plateau in the time profiles of S+ ions.
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