A theoretical study on the photodissociation mechanism of acetyl fluoride (CH3C(O)F) involving S-0, S-1, and T-1 states

doi:10.1016/j.chemphys.2017.05.003

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	A theoretical study on the photodissociation mechanism of acetyl fluoride (CH3C(O)F) involving S-0, S-1, and T-1 states
	Song, Xinli
刊名	CHEMICAL PHYSICS
	2017-07-10
卷号	491 页码:95-101
关键词	Photodissociation Dynamics Excited States Intersystem Crossing Acetyl Fluoride
DOI	10.1016/j.chemphys.2017.05.003
文献子类	Article
英文摘要	The dissociation potential energy surfaces of acetyl fluoride (CH3C(O)F) in the lowest three electronic states (S-0, S-1, and T-1) have been calculated at the CASPT2-f12/VTZ-f12 level of theory. Combining with the surface intersection points, four mechanistic channels have been elucidated, namely, intersystem crossing (ISC) to the T-1 state, internal conversion (IC) to the ground state, H-atom transfer, and direct dissociation along the S-1 pathway. Unlike other acetyl halides, it is found that the alpha-C-C bond cleavage in T-1 surface after ISC to yield ground-state products CH3((2)A') + COF((2)A') is the most probable mechanism upon the excitation at 248 nm, which agrees well with the experimental observation. Both the S-1 and T-1 potential energy surfaces are reported systematically for the first time. A comparison of the reactivity among CH3C(O)F, CH3C(O)Cl, CH3C(O)Br, CH3C(O)I and CH3C(O)CH3 has been made. (C) 2017 Elsevier B.V. All rights reserved.
WOS关键词	MULTIREFERENCE PERTURBATION-THEORY ; MOLECULAR-DYNAMICS ; ALPHA-BOND ; AB-INITIO ; 235 NM ; CHLORIDE ; EXCITATION ; CL ; PHOTOCHEMISTRY ; RADICALS
WOS研究方向	Chemistry ; Physics
语种	英语
WOS记录号	WOS:000404317700012
资助机构	National Natural Science Foundation of China(21503270) ; National Natural Science Foundation of China(21503270) ; National Natural Science Foundation of China(21503270) ; National Natural Science Foundation of China(21503270)
内容类型	期刊论文
源URL	[http://ir.wipm.ac.cn/handle/112942/11471]
专题	武汉物理与数学研究所_理论与交叉研究部
作者单位	Chinese Acad Sci, Wuhan Inst Phys & Math, State Key Lab Magnet Resonance & Atom & Mol Phys, Wuhan 430071, Peoples R China
推荐引用方式 GB/T 7714	Song, Xinli. A theoretical study on the photodissociation mechanism of acetyl fluoride (CH3C(O)F) involving S-0, S-1, and T-1 states[J]. CHEMICAL PHYSICS,2017,491:95-101.
APA	Song, Xinli.(2017).A theoretical study on the photodissociation mechanism of acetyl fluoride (CH3C(O)F) involving S-0, S-1, and T-1 states.CHEMICAL PHYSICS,491,95-101.
MLA	Song, Xinli."A theoretical study on the photodissociation mechanism of acetyl fluoride (CH3C(O)F) involving S-0, S-1, and T-1 states".CHEMICAL PHYSICS 491(2017):95-101.