1. Involvement of a low-lying Rydberg state in the ultrafast relaxation dynamics of ethylene.
- Author
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Champenois, Elio G., Shivaram, Niranjan H., Wright, Travis W., Chan-Shan Yang, Belkacem, Ali, and Cryan, James P.
- Subjects
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RYDBERG states , *PHOTOELECTRON spectroscopy , *POPULATION transfers , *MOLECULAR dynamics , *AB initio quantum chemistry methods , *ELECTRON kinetic energy , *INTERNAL conversion (Nuclear physics) , *ETHYLENE - Abstract
We present a measurement of the time-resolved photoelectron kinetic energy spectrum of ethylene using 156 nm and 260 nm laser pulses. The 156 nm pulse first excites ethylene to the ¹B1u (ππ*) electronic state where 260 nm light photoionizes the system to probe the relaxation dynamics with sub-30 fs resolution. Recent ab initio calculations by Mori et al. [J. Phys. Chem. A 116, 2808-2818 (2012)] have predicted an ultrafast population transfer from the initially excited state to a low-lying Rydberg state during the relaxation of photoexcited ethylene. The measured photoelectron kinetic energy spectrum reveals wave packet motion on the valence state and shows indications that the low-lying π3s Rydberg state is indeed transiently populated via internal conversion following excitation to the ππ* state, supporting the theoretical predictions. [ABSTRACT FROM AUTHOR]
- Published
- 2016
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