Laser photolysis, infrared fluorescence determination of CH3(nu3) vibrational deactivation by He, Ar, N2, CO, SF6, and (CH3)2CO

Journal Article · Thu Jun 04 04:00:00 EDT 1987 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100296a005· OSTI ID:6423679

Donaldson, D J; Leone, S R

Room temperature vibrational deactivation rate constants are reported for methyl radicals with antisymmetric stretch excitation, CH3(nu3) + M CH3 + M, where M = He, Ar, N2, CO, SF6, (CH3)2CO. Excimer laser photolysis of acetone at 193 nm is used to populate CH3(nu3), and time-resolved infrared emission from the CH stretch is used to follow the deactivation kinetics. The rate constants obtained are (+/-2sigma) (2.6 +/- 0.5) x 10 T (He, (6.8 +/- 0.7) x 10 T (Ar), (6.1 +/- 0.6) x 10 T (N2), (3.6 +/- 0.7) x 10 T (CO), (6.9 +/- 0.7) x 10 T (SF6), and (8.1 +/- 0.9) x 10 S (CH3COCH3) in units of cmT molecule s . The deactivation probability is not controlled by long-range forces due to the lone electron on the radical, but rather by the probabilities for intramode vibrational energy flow in CH3.

• Research Organization: Univ. of Colorado, Boulder
• OSTI ID: 6423679
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:12; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ACETONE
ALKYL RADICALS
ARGON
ATOM COLLISIONS
ATOM-MOLECULE COLLISIONS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTIONS
COLLISIONS
DATA
DE-EXCITATION
DECOMPOSITION
ELEMENTS
EMISSION SPECTROSCOPY
ENERGY LEVELS
ENERGY TRANSFER
ENERGY-LEVEL TRANSITIONS
EXCIMER LASERS
EXCITED STATES
EXPERIMENTAL DATA
FLUIDS
FLUORIDES
FLUORINE COMPOUNDS
GAS LASERS
GASES
HALIDES
HALOGEN COMPOUNDS
HELIUM
INFORMATION
KETONES
LASERS
METHYL RADICALS
MOLECULE COLLISIONS
NITROGEN
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADIATIONLESS DECAY
RADICALS
RARE GASES
SPECTROSCOPY
SULFUR COMPOUNDS
SULFUR FLUORIDES
VIBRATIONAL STATES