Very high resolution photofragmentation-translational spectroscopy
We have designed and constructed a new higher resolution molecular beam apparatus, specifically for studying laser induced dissociation under collision free conditions. The photochemistry of acetylene at 193 nm has been studied. By finding the maximum release of translational energy of the products C/sub 2/H and H, D/sub 0/(C/sub 2/H-H) was derived with high accuracy and precision. Resolved structure in the product's translational energy distribution sheds lights on the vibronic properties of the C/sub 2/H radical. The heat of formation of the vinyl radical was determined by studying the photodissociation of vinylbromide at 193 nm. The collision free unimolecular decomposition of three nitroalkanes: nitromethane, nitroethane and 2-nitropropane, was investigated using infrared multiphoton dissociation (IRMPD). The isomerization of CH/sub 3/NO/sub 2/ to CH/sub 3/ONO was observed for the first time and raises interesting questions about the primary decomposition pathways of other nitro-containing molecules. Through a novel application of RRKM theory, the barrier height to isomerization was found to be approx.5 kcal/mol lower than the C-N bond energy in nitromethane. 126 refs., 38 figs., 11 tabs.
- Research Organization:
- California Univ., Berkeley (USA)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 7100996
- Report Number(s):
- LBL-22619; ON: DE87004595
- Resource Relation:
- Other Information: Thesis. Portions of this document are illegible in microfiche products
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ACETYLENE
BINDING ENERGY
DISSOCIATION
PHOTOCHEMISTRY
BROMINE COMPOUNDS
ETHANE
NITRO COMPOUNDS
NITROMETHANE
ISOMERIZATION
PROPANE
VINYL RADICALS
FORMATION HEAT
MOLECULAR BEAMS
PHOTOCHEMICAL REACTIONS
TIME-OF-FLIGHT SPECTROMETERS
ALKANES
ALKYL RADICALS
ALKYNES
BEAMS
CHEMICAL EXPLOSIVES
CHEMICAL REACTIONS
CHEMISTRY
ENERGY
ENTHALPY
EXPLOSIVES
HALOGEN COMPOUNDS
HYDROCARBONS
MEASURING INSTRUMENTS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHYSICAL PROPERTIES
RADICALS
REACTION HEAT
SPECTROMETERS
THERMODYNAMIC PROPERTIES
400500* - Photochemistry
400201 - Chemical & Physicochemical Properties