High-temperature decomposition of tetramethyldioxetane: measurements of gas-phase chemiexcitation yields

Journal Article · Thu Jul 14 04:00:00 EDT 1988 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100325a022· OSTI ID:6334303

Tolbert, M A; Huestis, D L; Rossi, M J

The yields of electronically excited acetone from high-temperature decomposition of gas-phase tetramethyldioxetane (TMD) are reported. High temperatures are achieved by using infrared-sensitized excitation of TMD. Emission studies are used to obtain the yield of excited singlet acetone, /Phi//sub S/ = 0.017 (/plus minus/ 0.008). This value is approximately a factor of 2 higher than that reported in solution. A lower limit for the yield of triplet acetone is determined by using transient absorption studies, /Phi//sub T/ />=/ 0.10 (/plus minus/ 0.03). This value is comparable to previous results in solution. The lifetime of triplet acetone observed in the present experiment is approximately 5 ..mu..s, almost 2 orders of magnitude shorter than the lifetime of thermalized triplet acetone at low pressures. The short lifetime is attributed to electronic quenching by the infrared-absorbing gas CH/sub 3/F, with an estimated rate constant of 5 x 10/sup -13/ cm/sup 3//(molecule s).

• Research Organization: SRI International, Menlo Park, CA (USA)
• DOE Contract Number: W-7405-ENG-36
• OSTI ID: 6334303
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 92:14; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
42 ENGINEERING
420300 -- Engineering-- Lasers-- (-1989)
ACETONE
CHEMICAL LASERS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
DATA
DECOMPOSITION
DIOXIN
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
FLUIDS
FLUORIDES
FLUORINE COMPOUNDS
GASES
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
INFORMATION
KETONES
LASERS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
RYDBERG STATES
SULFUR COMPOUNDS
SULFUR FLUORIDES
YIELDS