Infrared laser induced multiphoton dissociation of decafluorocyclopentane in a concerted pathway: time resolved evidence of :CF/sub 2/ formation
The infrared multiphoton dissociation (IRMPD) of decafluorocyclopentane (DFCP) generates tetrafluoroethylene and difluorocarbene as the primary products. The :CF/sub 2/ dimerizes to form C/sub 2/F/sub 4/; the kinetics of the reaction is followed by monitoring the disappearance of :CF/sub 2/ absorption at 249 nm in real time after the CO/sub 2/ laser pulse, with a rate constant k/sub 2/ = 4.35 x 10/sup 7/ M/sup -1/ s/sup -1/. The vibrational temperature associated with the nascent :CF/sub 2/ is found to be 1100 K. The MPD yield of DFCP shows a strong fluence dependence, with a threshold of approx. 0.5 J/cm/sup 2/ for the 10 R(40) CO/sub 2/ laser line. The MPD spectra reveal two peaks, one 22 cm/sup -1/ red-shifted from the 989 cm/sup -1/ strong IR absorption band. Addition of SF/sub 6/ decreases the MPD yield.
- Research Organization:
- Bhabha Atomic Research Centre, Bombay, India
- OSTI ID:
- 5416444
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 92:1
- Country of Publication:
- United States
- Language:
- English
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ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CYCLOALKANES
PHOTOCHEMICAL REACTIONS
ORGANIC FLUORINE COMPOUNDS
REACTION INTERMEDIATES
CHEMICAL REACTION YIELD
ABSORPTION SPECTROSCOPY
CARBON DIOXIDE LASERS
CHEMICAL REACTION KINETICS
DISSOCIATION
EXPERIMENTAL DATA
INFRARED RADIATION
INFRARED SPECTRA
MULTI-PHOTON PROCESSES
ALKANES
CHEMICAL REACTIONS
DATA
ELECTROMAGNETIC RADIATION
GAS LASERS
HYDROCARBONS
INFORMATION
KINETICS
LASERS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
RADIATIONS
REACTION KINETICS
SPECTRA
SPECTROSCOPY
YIELDS
400500* - Photochemistry