Structure and energetics of C sub 2 H sub 4 Br sup + : Ethylenebromonium ion vs. bromoethyl cations
Journal Article
·
· Journal of the American Chemical Society; (United States)
- Univ. of Georgia, Athens (United States)
The cyclic and acyclic isomers of C{sub 2}H{sub 4}Br{sup +} are compared by using ab initio quantum mechanical techniques, including the use of electron correlation and polarization functions. The cyclic bromonium ion is found to be more stable than the acyclic 1-bromoethyl cation by 1.5 kcal/mol, in very good agreement with experiment. A transition state for the interconversion of these two forms is reported, the energy barrier being {approximately}25 kcal/mol. The relative energies of the cyclic and acyclic minima are remarkably insensitive to basis set and electron correlation effects, validating the results of previous low-level studies. The 2-bromoethyl cation does not exist as a minimum on the potential energy surface and spontaneously collapses to the bromonium ion upon torsion.
- DOE Contract Number:
- FG09-87ER13811
- OSTI ID:
- 5757633
- Journal Information:
- Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 112:23; ISSN 0002-7863; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BROMINATED ALIPHATIC HYDROCARBONS
CHARGED PARTICLES
CORRELATIONS
DATA
ELECTRON CORRELATION
ENERGY LEVELS
HALOGENATED ALIPHATIC HYDROCARBONS
HETEROCYCLIC COMPOUNDS
INFORMATION
IONS
MATHEMATICAL MODELS
MOLECULAR STRUCTURE
NUMERICAL DATA
ORGANIC BROMINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
THEORETICAL DATA
400201* -- Chemical & Physicochemical Properties
BROMINATED ALIPHATIC HYDROCARBONS
CHARGED PARTICLES
CORRELATIONS
DATA
ELECTRON CORRELATION
ENERGY LEVELS
HALOGENATED ALIPHATIC HYDROCARBONS
HETEROCYCLIC COMPOUNDS
INFORMATION
IONS
MATHEMATICAL MODELS
MOLECULAR STRUCTURE
NUMERICAL DATA
ORGANIC BROMINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
THEORETICAL DATA