Optical properties and sensing in plexcitonic nanocavities: from simple molecular linkers to molecular aggregate layers

We present a theoretical study of a metal-molecular aggregate hybrid system consisting of a strongly coupled dimer connected by molecules characterized by an excitonic transition. The plasmonic resonances of the metallic dimer interact with the molecular excitations giving rise to coupled plasmon-exciton states, so called plexcitons. We compare the differences in the optical response when the excitonic material is placed only as a linker in the plasmonic gap of the dimer and when the material is distributed as an aggregate layer covering the dimer entirely. We also explore the efficiency of plexcitons for localized surface plamon resonance (LSPR) sensing in both situations. The ordinary shift-based sensing is more efficient for dimers connected through molecular linkers, whereas intensity-based sensing is more effective when the molecular aggregate covers the entire nanostructure. These results can serve to design the chemistry of excitons around metallic nanoparticles. © 2014 IOP Publishing Ltd.
This project was supported by the Etortek project Nanoiker from the Basque Government (BG), project FIS2010-19609-C02-01 from the Spanish Ministry of Science and Innovation and grant IT-75613 from BG-UPV/EHU. OPG acknowledges financial support from Vicerrectorado de Investigación of the University of the Basque Country (Ayudas Especialización Doctores).