Strong mode-selective resonant vibrational excitation in chemisorbed molecules: an electron energy loss spectroscopy study of HCOO/GaAs (100)

Abstract

High resolution electron energy loss spectroscopy (HREELS) has been used to study the vibrational properties of the surface formate species (HCOO) chemisorbed on GaAs (100). Measurements carried out over a wide range of incident electron energies indicate that at least two of the vibrational modes of the adsorbate, namely the symmetric and asymmetric OCO stretches, are excited preferentially, even in specular scattering geometry, by a resonance scattering process involving formation of a temporary negative ion. The resonance, centred at ∼ 11 eV, is characterised by a large enhancement in the intensity of not only the fundamental vibrations, but also the appearance of a number of overtone and combination bands. The width and asymmetric profile of the resonance for the symmetric OCO stretch suggests there are two resonant states involved. The two final states, of a 1 and b 1 symmetry, correspond respectively to in-phase and out-of-phase combinations of the ƒ z 3 terms, based on the C-O bonds. The observation of both of these vibrational modes by resonance scattering suggests a breakdown of the mode-selective vibrational excitation selection rule.