Roaming in highly excited states: The central atom elimination of triatomic molecule decomposition

• 成果类型: Article
• 署名作者: Li, Zhenxing; Fu, Yan-lin; Luo, Zijie; Yang, Shuaikang; Wu, Yucheng; Wu, Hao; Wu, Guorong; Zhang, Weiqing; Fu, Bina; Yuan, Kaijun; Zhang, Donghui; Yang, Xueming
• 署名单位: Chinese Academy of Sciences; Dalian Institute of Chemical Physics, CAS; Dalian Maritime University; Chinese Academy of Sciences; University of Chinese Academy of Sciences, CAS; Southern University of Science & Technology; Hefei National Laboratory
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-11229
• DOI: 10.1126/science.adn3357
• 发表日期: 2024-02-16
• 页码: 746-750
• 关键词: sulfur-dioxide; photodissociation dynamics; dissociation; so2; acetaldehyde; mechanism; channels; path; no3

摘要

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(D-1)+O-2(a(1)Delta(g)), from SO2 photodissociation in highly excited states. The results revealed two dissociation pathways: One proceeds through the MEP to produce vibrationally colder O-2(a(1)Delta(g)) and the other yields vibrationally hotter O-2(a(1)Delta(g)) 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.