Variations of vibronic states in densely-packed structures of molecules with intramolecular dipoles

TL;DR

This study explores how electrostatic interactions influence vibronic states in densely packed molecular structures with dipoles, revealing environmental damping effects on molecular vibrations using advanced microscopy techniques.

Contribution

It demonstrates the impact of electrostatic environment on vibronic states in molecules with dipoles on a MoS₂ monolayer, a novel insight into molecular vibrations in such systems.

Findings

Vibronic states vary with molecular surroundings.

Electrostatic interactions damp molecular vibrations.

Dipole alignment influences vibronic intensity.

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 MoS$_2$ on Au(111) using scanning tunneling and atomic force microscopy and spectroscopy. These molecules exhibit a large dipole moment in gas phase, which we find to (partially) persist on the MoS$_2$ monolayer. The self-assembled structures consist of chains, where the dipoles of neighboring molecules are aligned anti-parallel. Thanks to the decoupling efficiency of the molecular states from the metal by the MoS$_2$ interlayer, we resolve vibronic states of the molecules, which vary in intensity depending on the molecular surrounding. We suggest that the vibrations are strongly damped by electrostatic interactions with the environment.