Adiabatic and Nonadiabatic Reaction Pathways of the O(P-3) with Propyne

doi:10.1021/jp8075707

CORC > 化学研究所 > 中国科学院化学研究所

	Adiabatic and Nonadiabatic Reaction Pathways of the O(P-3) with Propyne
	Zhao, Shaolei; Wu, Weiqiang; Zhao, Hongmei; Wang, Huan; Yang, Chunfan; Liu, Kunhui; Su, Hongmei
刊名	JOURNAL OF PHYSICAL CHEMISTRY A
	2009-01-08
卷号	113 期号:1 页码:23-34
ISSN号	1089-5639
DOI	10.1021/jp8075707
英文摘要	For the reaction of O(P-3) with propyne, the product channels and mechanisms are investigated both theoretically and experimentally. Theoretically, the CCSD(T)//B3LYP/6-311G(d,p) level of calculations are performed for both the triplet and singlet potential energy surfaces and the minimum energy crossing point between the two surfaces are located with the Newton-Lagrange method. The theoretical calculations show that the reaction occurs dominantly via the O-addition rather than the H-abstraction mechanism. The reaction starts with the O-addition to either of the triple bond carbon atoms forming triplet ketocarbene (CH3CCHO)-C-3 or (CH3COCH)-C-3 which can undergo decomposition, H-atom migration or intersystem crossing from which a variety of channels are open, including the adiabatic channels of CH3CCO + H (CH2CCHO + H), CH3 + HCCO, CH2CH + HCO, CH2CO + CH2, CH3CH + CO, and the nonadiabatic channels of C2H4 + CO, C2H2 + H-2 + CO, H-2 + H2CCCO. Experimentally, the CO channel is investigated with TR-FTIR emission spectroscopy. A complete detection of the CO product at each vibrationally excited level up to v = 5 is fulfilled, from which the vibrational energy disposal of CO is determined and found to consist with the statistical partition of the singlet C2H4 + CO channel, but not with the triplet CH3CH + CO channel. In combination with the present calculation results, it is concluded that CO arises mainly from the singlet methylketene ((CH3CHCO)-C-1) dissociation following the intersystem crossing of the triplet ketocarbene adduct ((CH3CCHO)-C-3). Fast intersystem crossing via the minimum energy crossing point of the triplet and singlet surfaces is shown to play significant roles resulting into nonadiabatic pathways for this reaction. Moreover, other interesting questions are explored as to the site selectivity of 0(3 P) atom being added to which carbon atom of the triple bond and different types of internal H-atom migrations including 1,2-H shift, 3,2-H shift, and 3,1-H shift involved in the reaction.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000262140100005
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/67423]
专题	中国科学院化学研究所
通讯作者	Su, Hongmei
作者单位	Chinese Acad Sci, Inst Chem, BNLMS, State Key Lab Mol React Dynam, Beijing 100190, Peoples R China
推荐引用方式 GB/T 7714	Zhao, Shaolei,Wu, Weiqiang,Zhao, Hongmei,et al. Adiabatic and Nonadiabatic Reaction Pathways of the O(P-3) with Propyne[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2009,113(1):23-34.
APA	Zhao, Shaolei.,Wu, Weiqiang.,Zhao, Hongmei.,Wang, Huan.,Yang, Chunfan.,...&Su, Hongmei.(2009).Adiabatic and Nonadiabatic Reaction Pathways of the O(P-3) with Propyne.JOURNAL OF PHYSICAL CHEMISTRY A,113(1),23-34.
MLA	Zhao, Shaolei,et al."Adiabatic and Nonadiabatic Reaction Pathways of the O(P-3) with Propyne".JOURNAL OF PHYSICAL CHEMISTRY A 113.1(2009):23-34.