Charged polycyclic aromatic hydrocarbons (PAHs), ultrasmall analogs of hydrogen-terminated graphene consisting of only a few fused aromatic carbon rings, have been shown to possess molecular plasmon resonances in the visible region of the spectrum. Unlike larger nanostructures, the PAH absorption spectra reveal rich, highly structured spectral features due to the coupling of the molecular plasmons with the vibrations of the molecule. Here, we examine this molecular plasmon-phonon interaction using a quantum mechanical approach based on the Franck-Condon approximation. We show that an independent boson model can be used to describe the complex features of the PAH absorption spectra, yielding an analytical and semiquantitative description of their spectral features. This investigation provides an initial insight into the coupling of fundamental excitations-plasmons and phonons-in molecules.
Keywords: PAHs; graphene; plasmonics; plasmon−phonon coupling; polyacenes.