标题：Dynamics Insight into Isomerization and Dissociation of Hot Criegee Intermediate CH3CHOO
作者：Wang, Zhiping; Dyakov, Yuri A.; Bu, Yuxiang
作者机构：[Wang, Zhiping] Shandong Univ, Sch Phys, Jinan 250100, Shandong, Peoples R China.; [Bu, Yuxiang] Shandong Univ, Sch Chem & Chem Engn, Jinan 250100, 更多
通讯作者：Bu, Yuxiang;Bu, YX;Bu, Yuxiang;Bu, Yuxiang
通讯作者地址：[Bu, YX]Shandong Univ, Sch Chem & Chem Engn, Jinan 250100, Shandong, Peoples R China.
来源：JOURNAL OF PHYSICAL CHEMISTRY A
摘要：We study the isomerization and dissociation of syn-CH3CHOO with high internal energies by combining electronic structure calculations, ab initio molecular dynamics, and RRKM microcanonical variational transition-state theories. The results show a striking effect of the internal energy on the reaction fate of syn-CH3CHOO. With lower internal energies, syn-CH3CHOO prefers isomerizing to vinyl hydroperoxide, which then produces hydroxyl radical. As the available internal energy increases, the O-elimination channel becomes more competitive and eventually the dominant channel. A third channel leading to methyl dioxirane is found to be less competitive than the former two. However, this channel is highly exothermic and produces greenhouse gases CH4 and CO2; thus, further investigation is needed to quantify its potential impact on the atmosphere. The present study provides new insight on clarifying the unimolecular reaction fate of hot syn-CH3CHOO and theoretical solutions for revealing the impact of internal energy on the complex gas phase reactions.