Inelastic electron tunneling spectroscopy (IETS) with the scanning tunneling microscope (STM) is a powerful technique used to characterize the vibration and spin states at the single-molecule level. While IETS lacks hard selection rules, historically it has been assumed that vibrational overtones are rarely seen or even absent. Here we provide definitive experimental evidence that the hindered rotation overtone excitation of carbon monoxide molecules adsorbed on Ag(110) can be detected with STM-IETS via isotope substitution. We also demonstrate that the anharmonicity of the overtone excitation can be characterized and compared between adsorption sites and find evidence of anisotropy in the vibrational anharmonicity for CO adsorbed on the [11[over ¯]0] step edge.
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