Kinetics of gas phase tetramethyldioxetane decomposition and chemiluminescence

Journal Article · Wed Nov 04 04:00:00 EST 1981 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00412a031· OSTI ID:5637823

Cannon, B D; Crim, F F

Pulsed-laser excitation of overtone vibrations or a weak electronic transition in gas-phase tetramethyldioxetane in combination with temporally and spectrally resolved detection of decomposition product luminescence reveals the presence, along with electronically excited acetone, of an additional emitting species which is not observed in solution studies. The emission is at shorter wavelengths than the acetone phosphorescence, and the emitting species has a zero-pressure decay rate of 0.019 +- 0.014 ..mu..s/sup -1/. The rapid collisional quenching which occurs on roughly every other encounter (k/sub q/ = 5.6 ..mu..s/sup -1/ torr/sup -1/) explains the inability of solution measurements to detect this feature of the tetramethyldioxetane decomposition kinetics. This newly observed component is likely to extend the interpretation of gas-phase decomposition experiments using infrared multiphoton absorption or collisions with fast Xe atoms to excite tetramethyldioxetane.

• Research Organization: Univ. of Wisconsin, Madison
• OSTI ID: 5637823
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 103:22; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
CHEMILUMINESCENCE
DATA
ELECTROMAGNETIC RADIATION
EXPERIMENTAL DATA
FLUIDS
GASES
INFORMATION
KINETICS
LASER RADIATION
LUMINESCENCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
RADIATIONS
REACTION KINETICS