Quantitative Understanding of the Optical Properties of a Single, Complex-Shaped Gold Nanoparticle from Experiment and Theory

We report on a combined study of Rayleigh and Raman scattering spectroscopy, 3D electron tomography, and discrete dipole approximation (DDA) calculations of a single, complex-shaped gold nanoparticle (NP). Using the exact reconstructed 3D morphology of the NP as input for the DDA calculations, the experimental results can be reproduced with unprecedented precision and detail. We find that not only the exact NP morphology but also the surroundings including the points of contact with the substrate are of crucial importance for a correct prediction of the NP optical properties. The achieved accuracy of the calculations allows determining how many of the adsorbed molecules have a major contribution to the Raman signal, a fact that has important Implications for analyzing experiments and designing sensing applications.