We
have measured the sticking probability of methane excited to
= 1 of the ν3 antisymmetric
C–H stretching vibration on a clean Ni(100) surface as a function of rotational state
(J
= 0, 1, 2 and 3) and have investigated the effect of Coriolis-mixing on reactivity.
The data span a wide range of kinetic energies (9–49 kJ mol−1) and indicate that rotational
excitation does not alter reactivity by more than a factor of two, even at low molecular speeds that allow for considerable rotation of the molecule during the interaction with the
surface. In addition, rotation-induced Coriolis-splitting of the ν3 mode into F+, F0 and
F− states does not significantly affect the reactivity for J
= 1 at 49 kJ mol−1 translational energy, even though the nuclear motions of these states differ. The lack of a pronounced
rotational energy effect in methane dissociation on Ni(100) suggests that our previous
results for (
= 1, ν3, J
= 2) are representative of all rovibrational sublevels of this vibrational
mode. These experiments shed light on the relative importance of rotational hindering and dynamical steering mechanisms in the dissociative chemisorption on Ni(100) and guide future attempts
to accurately
model methane dissociation
on nickel surfaces.
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