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
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
出版年:2019
卷:123
期:5
页码:1085-1090
DOI:10.1021/acs.jpca.8b11908
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.
收录类别:EI;SCOPUS;SCIE
资源类型:期刊论文
原文链接:https://www.scopus.com/inward/record.uri?eid=2-s2.0-85061152333&doi=10.1021%2facs.jpca.8b11908&partnerID=40&md5=2d9b671829d318b8ed8fe8c419178ce1
TOP