title: 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.
authors: Ecole Normale Supérieure de Lyon, Laboratoire de Chimie, CNRS UMR 5182, 46 Allée d'Italie, 69364 CEDEX07 Lyon, France.
authors: Shiri R
authors: SR
authors: Burema
authors: Ecole Normale Supérieure de Lyon, Laboratoire de Chimie, CNRS UMR 5182, 46 Allée d'Italie, 69364 CEDEX07 Lyon, France.
authors: Marie-Laure
authors: ML
authors: Bocquet
keywords: high-frequency stretching vibrations; inelastic electron tunneling spectroscopy (IETS); mesomeric forms; scanning tunneling microscopy (STM); single-molecule spectroscopy; vibrational selection rules; π electron density at metal−organic interface