Vibrational excitation of adsorbed molecules by low-energy photon-emitted electrons: A dynamical model

A simple, inelastic electron-scattering dynamical model is presented to account for vibrational excitation in molecular adsorbates. The basic two ingredients of the theoretical model are: (i) the conservation of the total angular momentum, and (ii) the requirement of a critical time to allow for the intra-molecular energy re-arrangement of the transient negative-ion complex. The model is applied to the vibrational excitation dynamics of molecules chemisorbed at sub-monolayer conditions on ordered metal surfaces. This was exemplified for Acrylonitrile adsorbed on Cu(1 0 0), whose vibrational excitation was studied via energy loss spectra of low-energy two-photon photoemission (2PPE) electrons, and for ammonia (NH3 and ND3) adsorbed on Cu(1 0 0), being probed in a STM experiment. Fits of the model to the data allowed for deducing the energy threshold of the vibrational excitation of the CC and CN bonds of the ACN adsorbate molecules, and the threshold for the symmetric ν1-stretch mode excitation of adsorbed NH3/ND3. Also, information about the temporal dynamics underlying the inelastic electron scattering was gained.