Photoinduced oxygen transfer from NO[sub 2] to ethylene in the vicinity of the NO[sub 2] dissociation threshold. A laser photochemical study on reactant pairs isolated in solid argon
Journal Article
·
· Journal of Physical Chemistry; (United States)
- Lawrence Berkeley Lab., CA (United States)
The wavelength dependence of the photochemistry of C[sub 2]H[sub 4]NO[sub 2] and C[sub 2]D[sub 2]NO[sub 2] paris, isolated in solid Ar, in the range 555-355 nm is reported. Continuous-wave and pulsed dye lasers were used to excite the reactants, and the products were monitored by FT infrared spectroscopy. Acetaldehyde, ethylene oxide, NO, and ethyl nitrite radical were the products observed at wavelengths longer than the 398-nm dissociation threshold of NO[sub 2]. D isotope effects on the branching among these species derived from kinetic analysis of growth curves support our conclusion in previous work that the mechanism involves large-amplitude O transfer from NO[sub 2] to the carbon-to-carbon double bond to yield a transient oxirane biradical. The latter acts as a common precursor of the observed products. A new species, ketene, appears at excitation energies just above the NO[sub 2] dissociation limit (385 and 355 nm). 55 refs., 8 figs., 1 tab.
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 6853109
- Journal Information:
- Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 96:25; ISSN JPCHAX; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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Transfer of CH[sub 2] from ketene to NO by photoexcitation of reactant pairs in solid argon below the CH[sub 2]=C=O dissociation limit
Journal Article
·
Thu Oct 18 00:00:00 EDT 1990
· Journal of Physical Chemistry; (USA)
·
OSTI ID:6234818
Photochemistry of cycloalkeneter dot NO sub 2 collisional pairs in a cryogenic matrix: Chemical trapping of cycloalkene oxirane biradical conformers, and comparison of product control for excitation above and below the NO sub 2 dissociation threshold
Journal Article
·
Wed Apr 03 23:00:00 EST 1991
· Journal of Physical Chemistry; (United States)
·
OSTI ID:5542857
Transfer of CH[sub 2] from ketene to NO by photoexcitation of reactant pairs in solid argon below the CH[sub 2]=C=O dissociation limit
Journal Article
·
Thu May 20 00:00:00 EDT 1993
· Journal of Physical Chemistry; (United States)
·
OSTI ID:6233983
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400500* -- Photochemistry
ACETALDEHYDE
ALDEHYDES
ALKENES
ARGON
CHALCOGENIDES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
DEUTERIUM COMPOUNDS
ELECTROMAGNETIC RADIATION
ELEMENTS
ETHYLENE
FLUIDS
GASES
HYDROCARBONS
HYDROGEN COMPOUNDS
INFRARED SPECTRA
KETENES
LASER RADIATION
NITRIC OXIDE
NITROGEN COMPOUNDS
NITROGEN DIOXIDE
NITROGEN OXIDES
NONMETALS
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
RADIATION EFFECTS
RADIATIONS
RARE GASES
SPECTRA
400102 -- Chemical & Spectral Procedures
400500* -- Photochemistry
ACETALDEHYDE
ALDEHYDES
ALKENES
ARGON
CHALCOGENIDES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
DEUTERIUM COMPOUNDS
ELECTROMAGNETIC RADIATION
ELEMENTS
ETHYLENE
FLUIDS
GASES
HYDROCARBONS
HYDROGEN COMPOUNDS
INFRARED SPECTRA
KETENES
LASER RADIATION
NITRIC OXIDE
NITROGEN COMPOUNDS
NITROGEN DIOXIDE
NITROGEN OXIDES
NONMETALS
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
RADIATION EFFECTS
RADIATIONS
RARE GASES
SPECTRA