Structure and energetics of simple carbenes CH/sub 2/, CHF, CHCl, CHBr, CF/sub 2/, and CCl/sub 2/

Journal Article · Wed Oct 26 04:00:00 EDT 1977 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00464a002· OSTI ID:5218617

Bauschlicher, Jr, C W; Schaefer, III, H F; Bagus, P S

There is very little experimental data concerning the singlet--triplet separations of carbenes. In many cases, it is not even possible to form estimates of this separation from experimental results. CH/sub 2/ is a distinct exception; here substantial, although contradictory, data are available. The equilibrium geometries of the lowest singlet states of several carbenes have been determined experimentally. However, the geometries of many states are not known and the triplet state geometries are also generally unknown. In order to obtain theoretical information about these quantities for a series of halogenated carbenes, we have studied CH/sub 2/, CHF, CHCl, CHBr, CF/sub 2/, and CCl/sub 2/ using a consistent level of ab initio electronic structure theory. One configuration (triplet state) and two configuration (singlet state) wave functions have been computed. Double zeta basis sets augmented by a d function on the carbon atom, optimized separately for both the singlet and triplet states of each molecule, were used. The theoretical equilibrium geometries agree well with the available experimental data. The trends of the singlet-triplet separations are discussed and correlated with the carbon atom Mulliken gross populations for the singlet and triplet states.

• Research Organization: Univ. of California, Berkeley
• OSTI ID: 5218617
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 99:22; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
BROMINATED ALIPHATIC HYDROCARBONS
CHLORINATED ALIPHATIC HYDROCARBONS
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
FLUORINATED ALIPHATIC HYDROCARBONS
HALOGENATED ALIPHATIC HYDROCARBONS
METHYLENE RADICALS
ORGANIC BROMINE COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
RADICALS