The Effect of Permanent Dipoles on Dark States in Molecular Dimers

Abstract: Many organic molecules possess large permanent dipole moments that differ depending on the electronic state. These permanent dipoles influence both intermolecular coupling and interactions with the optical fields, yet they are often neglected in typical theoretical quantum optics treatments. Here, we investigate the optical properties and their effect on dark states of dimers possessing such permanent dipoles. We show that when monomers have excitation-dependent permanent dipoles, optical transitions between the bright and dark states of the dimer are enabled. We investigate how permanent dipoles allow for the existence of static driving terms between the ground and excited states of each monomer. In turn, these can cause the excited states of the monomers to couple indirectly to the zero excitation state of the dimer. This leads to interference between permanent and transition dipoles and can result in the formation of dark states that are entirely localised. Furthermore, dark states formed through indirect coupling exhibit enhanced robustness against energy level fluctuations, which may improve the efficiency of the design of photovoltaic devices.