Resonance Charges to Encode Selection Rules in Inelastic Electron Tunneling Spectroscopy.

ABSTRACT

From extensive simulations of a set of covalently grafted phenyl derivatives onto Cu(111), we derive a simplistic rule that selectively predicts the onset of stretching vibrations in inelastic electron tunneling spectroscopy (IETS) with the scanning tunneling microscope. Indeed the rise (extinction) of the highest-frequency modes is found to correlate to the accumulation (depletion) of π electron density at the metal-organic contact point. This π electron density can be fine-tuned by the usage of (de) activating aromatic substituent at different ring positions. This finding provides a simple analysis tool that can be used to reveal structural characteristics on the atomic scale by IETS.