An integrated experimental and theoretical study on the optical properties of uniform hairy noble metal nanoparticles.

We report a viable route to plasmonic nanoparticles with well-controlled sizes, shapes, and compositions. A series of monodisperse Ag and Au nanoparticles capped with polystyrene chains (i.e., "hairy" nanoparticles) are crafted by capitalizing on star-like diblock copolymers as nanoreactors. Such monodisperse nanoparticles render an accurate absorption spectrum, providing a strong basis for theoretical investigation into their optical properties. By combining the experimental study with the three-dimensional finite element calculation of electromagnetic field distributions, the contributions of both intra-band and inter-band transitions to plasmonic absorption are revealed. The calculated absorption spectra perfectly reproduce the experimental observations, including the peak positions, shapes, and trends of peak shifting or broadening as a function of nanoparticle sizes. The influences of nanoparticle dimensions and surface ligands on plasmonic absorption of metallic nanoparticles are also systematically explored.