Ab initio study of rearrangements on the CH/sub 3/NO/sub 2/ potential energy surface
Journal Article
·
· J. Am. Chem. Soc.; (United States)
A theoretical study has been performed for the thermal rearrangements connecting nitromethane, methyl nitrite, nitrosomethanol, and aci-nitromethane by using the 6-31G* basis set to optimize geometries and introducing correlation at the MP2 level. The lowest calculated rearrangement pathways from nitromethane are to methyl nitrite (..delta..H/sup double dagger/ = 73.5 kcal/mol) and aci-nitromethane (..delta..H/sup double dagger/ = 75.0 kcal/mol). Nitrosomethanol, although predicted to be only 1.6 kcal/mol less stable, is separated by two high barriers from nitromethane. An elimination transition structure connecting methyl nitrite and formaldehyde plus nitroxyl is found to have an enthalpic barrier of 44.1 kcal/mol. Fragmentation reactions have enthalpies of reaction less than calculated barrier heights, suggesting that concerted rearrangements on the CH/sub 3/NO/sub 2/ surface in general will not be observed.
- Research Organization:
- Auburn Univ., AL
- OSTI ID:
- 5344922
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:19; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
Similar Records
MCSCF study of the rearrangement of nitromethane to methyl nitrite
Barrier widths, barrier heights, and the origins of anomalous kinetic H/D isotope effects
Ab initio study of the addition reaction of the methyl radical to ethylene and formaldehyde
Journal Article
·
Thu Oct 19 00:00:00 EDT 1989
· Journal of Physical Chemistry; (USA)
·
OSTI ID:6752481
Barrier widths, barrier heights, and the origins of anomalous kinetic H/D isotope effects
Journal Article
·
Wed May 23 00:00:00 EDT 1990
· Journal of the American Chemical Society; (USA)
·
OSTI ID:6879765
Ab initio study of the addition reaction of the methyl radical to ethylene and formaldehyde
Journal Article
·
Wed Mar 22 23:00:00 EST 1989
· Journal of Physical Chemistry; (USA)
·
OSTI ID:5113513
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500 -- Photochemistry
400800 -- Combustion
Pyrolysis
& High-Temperature Chemistry
500100 -- Environment
Atmospheric-- Basic Studies-- (-1989)
54 ENVIRONMENTAL SCIENCES
ALKANES
CHEMICAL EXPLOSIVES
CHEMICAL REACTIONS
CONFIGURATION INTERACTION
CONFORMATIONAL CHANGES
DATA
DECOMPOSITION
ENTHALPY
EXPLOSIVES
HYDROCARBONS
INFORMATION
NITRITES
NITRO COMPOUNDS
NITROGEN COMPOUNDS
NITROMETHANE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHYSICAL PROPERTIES
THEORETICAL DATA
THERMODYNAMIC PROPERTIES
THERMODYNAMICS
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500 -- Photochemistry
400800 -- Combustion
Pyrolysis
& High-Temperature Chemistry
500100 -- Environment
Atmospheric-- Basic Studies-- (-1989)
54 ENVIRONMENTAL SCIENCES
ALKANES
CHEMICAL EXPLOSIVES
CHEMICAL REACTIONS
CONFIGURATION INTERACTION
CONFORMATIONAL CHANGES
DATA
DECOMPOSITION
ENTHALPY
EXPLOSIVES
HYDROCARBONS
INFORMATION
NITRITES
NITRO COMPOUNDS
NITROGEN COMPOUNDS
NITROMETHANE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHYSICAL PROPERTIES
THEORETICAL DATA
THERMODYNAMIC PROPERTIES
THERMODYNAMICS