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Title: Involvement of a low-lying Rydberg state in the ultrafast relaxation dynamics of ethylene

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4939220· OSTI ID:22493615
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  1. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

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 {sup 1}B{sub 1u} (ππ{sup ∗}) 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{sup ∗} state, supporting the theoretical predictions.

OSTI ID:
22493615
Journal Information:
Journal of Chemical Physics, Vol. 144, Issue 1; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
Country of Publication:
United States
Language:
English