Hyperthermal reactions of O and O2 with a hydrocarbon surface: direct C-C bond breakage by O and H-atom abstraction by O2.
A C-C bond-breaking reaction has been observed when a beam containing hyperthermal oxygen was directed at a continuously refreshed saturated hydrocarbon liquid (squalane) surface. The dynamics of this C-C bond-breaking reaction have been investigated by monitoring time-of-flight and angular distributions of the volatile product, OCH3 or H2CO. The primary product is believed to be the methoxy radical, OCH3, but if this radical is highly internally excited, then it may undergo secondary dissociation to form formaldehyde, H2CO. Either the primary or the secondary product may scatter directly into the gas phase before thermal equilibrium with the surface is reached, or they may become trapped on the surface and desorb in thermal equilibrium with the surface. Direct, single-collision scattering events that produce a C-C bond-breaking product are described with a kinematic picture that allows the determination of the effective surface mass encountered by an incident O atom, the atom-surface collision energy in the center-of-mass frame, and the fraction of the center-of-mass collision energy that goes into translation of the scattered gaseous product and the recoiling surface fragment. The dynamical behavior of the C-C bond-breaking reaction is compared with that of the H-atom abstraction reaction, which was the subject of an earlier study. Another reaction, H-atom abstraction by O2 (which is present in the hyperthermal beam), has also been observed, and the dynamics of this reaction are compared with the inelastic scattering dynamics of O2 and the dynamics of H-atom abstraction by O. The dynamics involving direct inelastic and reactive scattering of O2 are also described in terms of a kinematic picture where the incident O2 molecule is viewed as interacting with a local region of the surface.
Zhang
Jianming
J
Department of Chemistry and Biochemistry, Montana State University, Bozeman, Montana 59717, USA.
Upadhyaya
Hari P
HP
Brunsvold
Amy L
AL
Minton
Timothy K
TK