In the interaction of low energy F-2 with Si(100) at 250 K, a dissociative
chemisorption mechanism called atom abstraction is identified in which only
one of the F atoms is adsorbed while the other F atom is scattered into th
e gas phase. The dynamics of atom abstraction are characterized via time-of
-flight measurements of the scattered F atoms. The F atoms are translationa
lly hyperthermal but only carry a small fraction (similar to 3%) of the tre
mendous exothermicity of the reaction. The angular distribution of F atoms
is unusually broad for the product of an exothermic reaction. These results
suggest an "attractive" interaction potential between F-2 and the Si dangl
ing bond with a transition state that is not constrained geometrically. The
se results are in disagreement with the results of theoretical investigatio
ns implying that the available potential energy surfaces are inadequate to
describe the dynamics of this gas-surface interaction. In addition to singl
e atom abstraction, two atom adsorption, a mechanism analogous to classic d
issociative chemisorption in which both F atoms are adsorbed onto the surfa
ce, is also observed. The absolute probability of the three scattering chan
nels (single atom abstraction, two atom adsorption, and unreactive scatteri
ng) for an incident F-2 are determined as a function of F-2 exposure. The f
luorine coverage is determined by integrating the reaction probabilities ov
er F-2 exposure, and the reaction probabilities are recast as a function of
fluorine coverage. Two atom adsorption is the dominant channel [P-2 = 0.83
+/- 0.03(95%, N=9)] in the limit of zero coverage and decays monotonically
to zero. Single atom abstraction is the minor channel (P-1 = 0.13 +/- 0.03
) at low coverage but increases to a maximum (P-1 = 0.35 +/- 0.08) at about
0.5 monolayer (ML) coverage before decaying to zero. The reaction ceases a
t 0.94 +/- 0.11(95%, N = 9) ML. Thermal desorption and helium diffraction c
onfirm that the dangling bonds are the abstraction and adsorption sites. No
Si lattice bonds are broken, in contrast to speculation by other investiga
tors that the reaction exothermicity causes lattice disorder. (C) 1999 Amer
ican Institute of Physics. [S0021-9606(99)70431-9].