CH bond activation in CH sub 4 and t-BuO(ads) by oxygen chemisorbed on Ag(110). Molecular orbital theory
Journal Article
·
· Journal of the American Chemical Society; (United States)
- Case Western Reserve Univ., Cleveland, OH (USA)
Activation of the CH bond in CH{sub 4} and t-BuO(ads) by H{sup {sm bullet}} transfer to O adsorbed on the Ag(110) surface has been studied by the atom-superposition and electron-delocalization molecular orbital theory. Both abstractions are found to proceed with a low-energy barrier because of the presence of low-lying empty Ag surface orbitals at the Fermi level. Transfer of an electron to the Fermi level alleviates the initial closed-shell repulsion between the CH {sigma}-bond electron pair and the surface O (which is formally O{sup 2{minus}}) lone-pair orbital that ultimately forms the OH {sigma} bond. It is concluded that surface O behaves like a radical anion O{sup {sm bullet}{minus}} or R{sub 3}O{sup {sm bullet}} in its ability to form a single bond. These calculations also suggest the possibility that surface oxygen atoms might insert into CH bonds to form alcohols, which is a result of their ability to exhibit O atom or carbene (R{sub 2}C:) bonding properties.
- OSTI ID:
- 5379754
- Journal Information:
- Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 112:20; ISSN 0002-7863; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
09 BIOMASS FUELS
091000* -- Biomass Fuels-- Properties & Composition-- (1990-)
10 SYNTHETIC FUELS
100300 -- Synthetic Fuels-- Properties & Composition-- (1990-)
ALKANES
CALCULATION METHODS
CATALYSTS
CHEMICAL ACTIVATION
CHEMICAL REACTIONS
CHEMISORPTION
DATA
ELEMENTS
ENERGY LEVELS
FERMI LEVEL
HYDROCARBONS
INFORMATION
METALS
METHANE
MOLECULAR ORBITAL METHOD
NUMERICAL DATA
ORGANIC COMPOUNDS
SEPARATION PROCESSES
SILVER
SORPTION
THEORETICAL DATA
TRANSITION ELEMENTS
091000* -- Biomass Fuels-- Properties & Composition-- (1990-)
10 SYNTHETIC FUELS
100300 -- Synthetic Fuels-- Properties & Composition-- (1990-)
ALKANES
CALCULATION METHODS
CATALYSTS
CHEMICAL ACTIVATION
CHEMICAL REACTIONS
CHEMISORPTION
DATA
ELEMENTS
ENERGY LEVELS
FERMI LEVEL
HYDROCARBONS
INFORMATION
METALS
METHANE
MOLECULAR ORBITAL METHOD
NUMERICAL DATA
ORGANIC COMPOUNDS
SEPARATION PROCESSES
SILVER
SORPTION
THEORETICAL DATA
TRANSITION ELEMENTS