Quantifying the Plasmonic Character of Optical Excitations in a Molecular J-Aggregate

TL;DR

This paper investigates whether the intense optical absorption in molecular J-aggregates exhibits plasmonic character, using first-principles simulations and a theoretical model to distinguish plasmonic from nonplasmonic excitations.

Contribution

It introduces a computational approach to assess plasmonicity in molecular aggregates and demonstrates that J-aggregates' excitations are nonplasmonic despite strong absorption.

Findings

Aggregation lowers the generalized plasmonicity index (GPI) of the J-band.

J-aggregate excitations are shown to be nonplasmonic.

A simplified model helps distinguish collective excitations from plasmons.

Abstract

The definition of plasmon at the microscopic scale is far from being understood. Yet, it is very important to recognize plasmonic features in optical excitations, as they can inspire new applications and trigger new discoveries by analogy with the rich phenomenology of metal nanoparticle plasmons. Recently, the concepts of plasmonicity index and the generalized plasmonicity index (GPI) have been devised as computational tools to quantify the plasmonic nature of optical excitations. The question may arise whether any strong absorption band, possibly with some sort of collective character in its microscopic origin, shares the status of plasmon. Here we demonstrate that this is not always the case, by considering a well-known class of systems represented by J-aggregates molecular crystals, characterized by the intense J band of absorption. By means of first-principles simulations, based on a many-body perturbation theory formalism, we investigate the optical properties of a J-aggregate made of push-pull organic dyes. We show that the effect of aggregation is to lower the GPI associated with the J-band with respect to the isolated dye one, which corresponds to a nonplasmonic character of the electronic excitations. In order to rationalize our finding, we then propose a simplified one-dimensional theoretical model of the J-aggregate. A useful microscopic picture of what discriminates a collective molecular crystal excitation from a plasmon is eventually obtained.