Vibronic excitation of oxygen-atom transfer from NO sub 2 to ethylene by long-wavelength visible light in a cryogenic matrix

Journal Article · Thu Oct 18 04:00:00 EDT 1990 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100384a035· OSTI ID:6234818

Nakata, Munetaka; Frei, Heinz ^[1]; Shibuya, Kazuhiko ^[2]

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1. Lawrence Berkeley Lab., CA (USA)
2. Tokyo Institute of Technology (Japan)

Chemical reaction has been observed upon irradiation of ethylene{center dot}NO{sub 2} pairs in solid Ar with continuous-wave dye laser light at visible wavelengths as long as 574 nm, well below the 398-nm dissociation limit of isolated NO{sub 2}. Reaction products were acetaldehyde, ethylene oxide, NO, and ethyl nitrite radical, as established by FT infrared spectroscopy. Kinetic analysis of product absorbance growth showed that acetaldehyde is the prevalent final oxidation product of direct, single-photon photolysis of ethylene{center dot}{sub 2} pairs, while ethylene oxide is exclusively produced by yellow and shorter wavelength induced photodissociation of trapped ethyl nitrite radical. Experiments with trans- and cis-CHD{double bond}CHD yielded nitrite radical CHD-CHD-ONO under retention of stereochemistry but with scrambling in the epoxide product. On the basis of these results and those of their earlier work on NO{sub 2} photooxidation of cis- and trans-2-butene, a reaction path is proposed that involves O-atom transfer from NO{sub 2} to the C{double bond}C bond to give a short-lived singlet oxirane biradical. The photolysis wavelength dependence of the reaction quantum efficiency indicates that NO{sub 2} reactant vibrational excitation plays an essential role and opens a reaction path that is unique to visible light induced alkene + NO{sub 2} chemistry in a matrix.

• DOE Contract Number: AC03-76SF00098
• OSTI ID: 6234818
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 94:21; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
CHALCOGENIDES
CHEMICAL REACTIONS
DATA
DYE LASERS
EXPERIMENTAL DATA
INFORMATION
INFRARED SPECTRA
KINETICS
LASERS
LIQUID LASERS
NITROGEN COMPOUNDS
NITROGEN OXIDES
NITROXYL RADICALS
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
RADICALS
REACTION KINETICS
SPECTRA