Resonant Frequency Distributions Determine Plasmonic Response of Disordered Nanoparticle Ensembles

Understanding how colloidal soft materials interact with light is crucial to rational design of optical metamaterials. Electromagnetic simulations are computationally expensive and have primarily been limited to model systems described by a small number of particles -- dimers, small clusters, and small periodic unit cells of superlattices. In this work, we study the optical properties of bulk, disordered soft materials comprising a large number of plasmonic colloidal nanoparticles using Brownian dynamics simulations and the mutual polarization method. We investigate the far-field and near-field optical properties of both colloidal fluids and gels, which require thousands of nanoparticles to describe statistically. We show that these disordered materials exhibit a distribution of particle-level plasmonic resonance frequencies that determines their optical response. Nanoparticles with similar resonant frequencies form anisotropic and oriented clusters embedded within the otherwise isotropic and disordered microstructures. These collectively resonating morphologies can be tuned with the frequency and polarization of incident light. Knowledge of particle resonant distributions may help to interpret and compare the optical responses of different colloidal structures, correlate and predict optical properties, and rationally design soft materials for applications harnessing light.