The interaction of state-selected and oriented N2O molecules with one monol
ayer of Li on Rh(100) was studied by means of exoelectron emission analysis
, time-of-flight mass spectroscopy and sticking measurements in a pulsed mo
lecular beam experiment. State-selected and oriented N2O molecules are prep
ared using electrostatic hexapole and dipole fields applying the linear Sta
rk effect. The sticking probability of N2O on Li/Rh(100) is found to be ind
ependent of the molecular state and orientation. The exoemission response o
n the pulsed beam reveals two different reaction channels: A direct channel
which coincides with the arrival of the gas pulse and an indirect channel
after the arrival of the gas pulses. The exoemission probability in the dir
ect channel is strongly enhanced for vibrationally excited N2O molecules an
d further increases when N2O hits the surface with the O-end first. Further
more, it is associated with the backscattering of N-2 molecules which depen
ds on the molecular orientation, as well. From these observations we identi
fy the direct reaction channel with an Eley-Rideal mechanism, i.e. an abstr
action reaction that proceeds during the impact of the N2O where 'harpoonin
g' is the key step that triggers the reaction. The indirect reaction channe
l, on the other hand, follows the Langmuir-Hinshelwood scheme where the rea
cting molecules are adsorbed on the surface with complete energy accommodat
ion and thus lose the information on their molecular state and orientation
in the gas phase. (C) 1999 Elsevier Science B.V. All rights reserved.