Further insight in the surprisingly complex unimolecular fragmentations of the methyl nitrite radical cation

Journal Article · Wed Jul 13 00:00:00 EDT 1994 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00093a046· OSTI ID:7178445

Schroeder, D; Schwarz, H ^[1]; Suelzle, D; Dutuit, O ^[2]; Baer, T ^[3]

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1. Technischen Universitaet Berlin (Germany)
2. Universite Paris-Sud (France)
3. Univ. of North Carolina, Chapel Hill, NC (United States)

The unimolecular fragmentation of deuterium and oxygen [sup 18]O isotopomers of the methyl nitrite radical cation (CH[sub 3]ONO[sup +]) was examined by means of tandem mass spectrometry. The [D[sub 1]] and [D[sub 2]] isotopomers were found to exhibit enormous intramolecular kinetic isotope effects associated with unimolecular H/D losses. The dissociation rates and breakdown diagrams of energy-selected CH[sub 3]ONO[sup +] and CD[sub 3]ONO[sup +] ions were measured by photoelectron photoion coincidences. These data exhibit a modest isotope effect. The experimental results imply that the unimolecular H and NO eliminations occur via a common intermediate, for which we suggest the distonic ion CH[sub 2]O(H)NO[sup +]. A new ionization energy of 10.44 eV for methyl nitrite is derived. Based on the experimental findings and the results of exploratory ab initio MO calculations, two models are presented for the unimolecular dissociation of the methyl nitrite radical cation, in which the initial step involves a 1,2-hydrogen atom migration, CH[sub 3]ONO[sup +] [yields] CH[sub 2]O(H)NO[sup +]. 27 refs., 4 figs., 3 tabs.

• OSTI ID: 7178445
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 116:14; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
99 GENERAL AND MISCELLANEOUS
990200 -- Mathematics & Computers
CALCULATION METHODS
CATIONS
CHARGED PARTICLES
COMPILED DATA
COMPUTERIZED SIMULATION
DATA
DEUTERIUM COMPOUNDS
DISSOCIATION
EVEN-EVEN NUCLEI
HYDROGEN COMPOUNDS
INFORMATION
IONIZATION
IONS
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
MASS SPECTROSCOPY
MOLECULAR ORBITAL METHOD
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
OXYGEN 18
OXYGEN ISOTOPES
RADICALS
REACTION INTERMEDIATES
REACTION KINETICS
SIMULATION
SPECTROSCOPY
STABLE ISOTOPES