Abstract
The role of the tip in inelastic electron tunneling spectroscopy (IETS) performed with scanning tunneling microscopes (STM) is theoretically addressed via first-principles simulations of vibrational spectra of single carbon monoxide (CO) molecules adsorbed on Cu(111). We show how chemically functionalized STM tips modify the IETS intensity corresponding to adsorbate modes on the sample side. The underlying propensity rules are explained using symmetry considerations for both the vibrational modes and the molecular orbitals of the tip and sample. This suggests that single-molecule IETS can be optimized by selecting the appropriate tip orbital symmetry.
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