Variations of Vibronic States in Densely Packed Structures of Molecules with Intramolecular Dipoles

Abstract

Electrostatic potentials strongly affect molecular energy levels and charge states, providing the fascinating opportunity of molecular gating. Their influence on molecular vibrations remains less explored. Here, we investigate ethyl‐diaminodicyanoquinone molecules on a monolayer of MoS2 on Au(111) using scanning tunneling and atomic force microscopy and spectroscopy. These molecules exhibit a large dipole moment in gas phase, which is found to (partially) persist on the MoS2 monolayer. The self‐assembled structures consist of chains, where the dipoles of neighboring molecules are aligned antiparallel. Thanks to the decoupling efficiency of the molecular states from the metal by the MoS2 interlayer, vibronic states of the molecules are resolved, which vary in intensity depending on the molecular surrounding. We suggest that the vibrations are strongly damped by electrostatic interactions with the environment.