Competition between atomic and molecular chlorine elimination in the infrared multiphoton dissociation of CF/sub 2/Cl/sub 2/

Journal Article · Wed Dec 15 00:00:00 EST 1982 · J. Chem. Phys.; (United States)

OSTI ID:6559250

Krajnovich, D; Huisken, F; Zhang, Z; Shen, Y R; Lee, Y T

Infrared multiphoton dissociation of CF/sub 2/Cl/sub 2/ has been reinvestigated by the crossed laser-molecular beam technique using a high repetition rate CO/sub 2/ TEA laser. Both the atomic and molecular chlorine elimination channels were observed: (1) CF/sub 2/Cl/sub 2/..-->..CF/sub 2/Cl+Cl and (2) CF/sub 2/Cl/sub 2/..-->..CF/sub 2/+Cl/sub 2/. No evidence was found for secondary dissociation of CF/sub 2/Cl at laser energy fluences up to 8 J/cm/sup 2/. Center-of-mass product translational energy distributions were obtained for both dissociation channels. In agreement with previous work, the products of reaction (1) are found to have a statistical translational energy distribution. The products of reaction (2) are formed with a mean translational energy of 8 kcal/mol, and the distribution peaks rather sharply about this value, indicating a sizeable exit barrier to molecular elimination. The product branching ratio was directly determined. Reaction (2) accounts for roughly 10% of the total dissociation yield in the fluence range 0.3--8 J/cm/sup 2/. These results provide an additional test of the statistical theory of unimolecular reactions.

• Research Organization: Materials and Molecular Research Division, Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720
• OSTI ID: 6559250
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 77:12; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640304* -- Atomic
Molecular & Chemical Physics-- Collision Phenomena
74 ATOMIC AND MOLECULAR PHYSICS
BEAMS
CARBON DIOXIDE LASERS
CHEMICAL REACTIONS
CHLORINATED ALIPHATIC HYDROCARBONS
COLLISIONS
DECOMPOSITION
DISSOCIATION
ELECTROMAGNETIC RADIATION
FLUORINATED ALIPHATIC HYDROCARBONS
GAS LASERS
HALOGENATED ALIPHATIC HYDROCARBONS
INFRARED RADIATION
LASER RADIATION
LASERS
MOLECULAR BEAMS
MOLECULE COLLISIONS
MULTI-PHOTON PROCESSES
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PHOTON COLLISIONS
PHOTON-MOLECULE COLLISIONS
RADIATIONS