Bond selective photochemistry in CH/sub 2/BrI through electronic excitation at 210 nm

Journal Article · Tue Apr 01 00:00:00 EST 1986 · J. Chem. Phys.; (United States)

OSTI ID:6143310

Butler, L J; Hintsa, E J; Lee, Y T

To explore the possibility of bond selective photochemistry in an excited electronic state, we have studied the photolysis of CH/sub 2/BrI in a molecular beam at 210 nm. Following the direct local excitation of a repulsive transition on the C--Br bond at 210 nm, the fragments were detected by time-of-flight mass spectrometry. The dominant channel was found to be C--Br fission (60%) releasing an average of 15 kcal/mol into translation with the remainder reacting to form CH/sub 2/+IBr and CH/sub 2/+I+Br. There was no evidence for the primary fission of the C--I bond, making this the first clear example of the selective cleavage of a stronger bond in a molecule over the weakest one.

• Research Organization: Materials and Molecular Research Division, Lawrence Berkeley Laboratory and Department of Chemistry, University of California, Berkeley, California 94720
• OSTI ID: 6143310
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 84:7; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
BEAMS
BROMINATED ALIPHATIC HYDROCARBONS
CHEMICAL BONDS
CHEMICAL REACTIONS
DECOMPOSITION
ELECTROMAGNETIC RADIATION
HALOGENATED ALIPHATIC HYDROCARBONS
IODINATED ALIPHATIC HYDROCARBONS
MASS SPECTROSCOPY
MOLECULAR BEAMS
ORGANIC BROMINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC IODINE COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADIATIONS
SPECTROSCOPY
ULTRAVIOLET RADIATION