Collective vibrations in cluster models for semiconductor surfaces: Vibrational spectra of acetylenyl and methylacetylenyl functionalized Si(111)

The geometries and harmonic vibrational frequencies of the acetylenyl and methylacetylenyl functionalized Si(111) surfaces are investigated using quantum chemical calculations. The vibrational spectra are computed using a previously introduced method whereby the collective vibrational modes that correspond to the vibrations of the infinite periodic system are derived from modest sized cluster models. Our predictions should be useful for the interpretation of the experimental spectra when they become available. The symmetry elements of the methylacetylenyl Si(111) surface that are derived from the space group of the optimized structure and a vibrational mode resulting from photon-adsorbate coupling are explored.