First-Principle Calculations of the Experimental Vibrational Spectrum of a Surface Adsorbate: Anharmonic Resonance Coupling between Fundamental and Binary Modes

By including relevant physical properties in our modeling of a surface adsorbate system we can, from first principles, correctly calculate all experimentally observed features in the vibrational spectrum of CH₃CH₂O- and CD₃CH₂O- adsorbed on Cu(100). That is, we reproduce the number of observed modes, the vibrational frequencies, and intensities of the modes including the presence/absence of binary overtone and combination modes. No scaling was performed. Our calculations show that the anharmonic terms of the potential energy surface of free ethanol are transferrable to the corresponding surface adsorbate, ethoxy, while the harmonic terms are not.