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The optical response of metal nanoparticles is governed by plasmonic resonances, which are dictated by the particle morphology. A thorough understanding of the link between morphology and optical response requires quantitatively measuring optical and structural properties of the same particle. Here we present such a study, correlating electron tomography and optical micro-spectroscopy. The optical measurements determine the scattering and absorption cross-section spectra in absolute units, and electron tomography determines the 3D morphology. Numerical simulations of the spectra for the individual particle geometry, and the specific optical set-up used, allow for a quantitative comparison including the cross-section magnitude. Silver nanoparticles produced by photochemically driven colloidal synthesis, including decahedra, tetrahedra and bi-tetrahedra are investigated. A mismatch of measured and simulated spectra is found in some cases when assuming pure silver particles, which is explained by the presence of a few atomic layers of tarnish on the surface, not evident in electron tomography. The presented method tightens the link between particle morphology and optical response, supporting the predictive design of plasmonic nanomaterials.

The optical response of metal nanoparticles is governed by plasmonic resonances, which depend often intricately on the geometry and composition of the particle and its environment. In this work we describe a method and analysis pipeline unravelling these relations at the single nanoparticle level through a quantitative characterization of the optical and structural properties. It is based on correlating electron microscopy with microspectroscopy measurements of the same particle immersed in media of different refractive indices. The optical measurements quantify the magnitude of both the scattering and the absorption cross sections, while the geometry measured in electron microscopy is used for numerical simulations of the cross section spectra accounting for the experimental conditions. We showcase the method on silver nanocubes of nominal 75 nm edge size. The large amount of information afforded by the quantitative cross section spectra and measuring the same particle in two environments, allows us to identify a specific degradation of the cube surface. We find a layer of tarnish, only a few nanometers thick, a fine surface compositional change of the studied system which would be hardly quantifiable otherwise.