Dissociation dynamics of perhaloalkoxy radicals

Journal Article · Wed Jul 19 04:00:00 EDT 1989 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00197a024· OSTI ID:6971350

Li, Zhuangjie; Francisco, J S ^[1]

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1. Wayne State Univ., Detroit, MI (USA)

The dissociation dynamics of CCl{sub 3-x}F{sub x}O radicals have been studied by using ab initio molecular orbital theory. The ab initio calculations suggest that chlorine atom elimination reactions from CCl{sub 3-x}F{sub x}O are low activation barrier processes, which dominate over fluorine atom dissociation processes. Calculated dissociation rate constants for both Cl and F elimination reactions predict a lifetime that is less than 10{sup {minus}10} s for the CCl{sub 3-x}F{sub x}O radicals. Replacement of two chlorine atoms by two fluorine atoms is found to stabilize the CCl{sub 3-x}F{sub x}O radicals. The atmospheric implication of these calculations is discussed.

• OSTI ID: 6971350
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:15; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
54 ENVIRONMENTAL SCIENCES
540110
ALKOXY RADICALS
ATMOSPHERIC CHEMISTRY
CALCULATION METHODS
CHEMISTRY
CHLORINE
DATA ANALYSIS
DISSOCIATION
ELEMENTS
FLUORINE
HALOGENS
KINETICS
MATHEMATICAL MODELS
MOLECULAR MODELS
NONMETALS
OZONE
PHOTOCHEMISTRY
RADICALS
REACTION KINETICS