We investigated the translational incidence energy (Ei) and surface temperature (Ts) dependence of CO vibrational excitation upon scattering from a clean Au(111) surface. We report absolute v = 0 → 1 excitation probabilities for Ei between 0.16 and 0.84 eV and Ts between 473 and 973 K. This is now only the second collision system where such comprehensive measurements are available – the first is NO on Au(111). For CO on Au(111), vibrational excitation occurs via direct inelastic scattering through electron hole pair mediated energy transfer – it is enhanced by incidence translation and the electronically non-adiabatic coupling is about 5 times weaker than in NO scattering from Au(111). Vibrational excitation via the trapping desorption channel dominates at Ei = 0.16 eV and quickly disappears at higher Ei.

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