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Updated: Jul 3, 2025

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
Roaming in highly excited states: The central atom elimination of triatomic molecule decomposition
Zhenxing Li1, Yan-Lin Fu1, Zijie Luo1,2
1State Key Laboratory of Molecular Reaction Dynamics and Dalian Coherent Light Source, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, P. R. China.
Abstract:
Chemical reactions are generally assumed to proceed from reactants to products along the minimum energy path (MEP). However, straying from the MEP-roaming-has been recognized as an unconventional reaction mechanism and found to occur in both the ground and first excited states. Its existence in highly excited states is however not yet established. We report a dissociation channel to produce electronically excited fragments, S(1D)+O2(a1Δg), from SO2 photodissociation in highly excited states. The results revealed two dissociation pathways: One proceeds through the MEP to produce vibrationally colder O2(a1Δg) and the other yields vibrationally hotter O2(a1Δg) by means of a roaming pathway involving an intramolecular O abstraction during reorientation motion. Such roaming dynamics may well be the rule rather than the exception for molecular photodissociation through highly excited states.
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