The electronic structure of molecules on metal surfaces is largely determined by hybridization and screening by the substrate electrons. As a result, the energy levels are significantly broadened and molecular properties, such as vibrations are hidden within the spectral line shapes. Insertion of thin decoupling layers reduces the line widths and may give access to the resolution of electronic and vibronic states of an almost isolated molecule. Here, we use scanning tunneling microscopy and spectroscopy to show that a single layer of MoS2 on Ag(111) exhibits a semiconducting bandgap, which may prevent molecular states from strong interactions with the metal substrate. We show that the lowest unoccupied molecular orbital (LUMO) of tetracyanoquinodimethane (TCNQ) molecules is significantly narrower than on the bare substrate and that it is accompanied by a characteristic satellite structure. Employing simple calculations within the Franck–Condon model, we reveal their vibronic origin and identify the modes with strong electron–phonon coupling.
