Light Scattering versus Plasmon Effects: Optical Transitions in Molecular Oxygen near a Metal Nanoparticle

The localized surface plasmon of a metal nanoparticle can influence the optical properties of a molecule in the plasmon field. In a previous study of molecular oxygen adjacent to nanodisks on a flat substrate, we showed that a plasmon field can increase the probability of the O₂(a¹Δ_g) → O₂(X³Σ_g^–) radiative transition at 1275 nm. For the present study, we set out to ascertain if metal nanoparticles suspended in a liquid solvent could likewise induce measurable plasmonic effects on optical transitions in oxygen. Metal nanoparticles were prepared with the intent of selectively perturbing the 765 nm O₂(X³Σ_g^–) → O₂(b¹Σ_g⁺) absorption transition. Because O₂(b¹Σ_g⁺) efficiently decays to O₂(a¹Δ_g), we used the spectrally distinct O₂(a¹Δ_g) → O₂(X³Σ_g^–) phosphorescent transition at 1275 nm to probe the potential plasmon effects at 765 nm. Although we indeed observed nanoparticle-mediated effects on the O₂(X³Σ_g^–) → O₂(b¹Σ_g⁺) transition, our present data are readily explained in terms of a nanoparticle-dependent change in the path length of light propagation through the sample. We modeled the latter using features of radiative transfer theory. As such, we cannot claim to observe a plasmonic effect on oxygen from these nanoparticles suspended in solution. Instead, our results point to the general importance of considering the effects of light scattering, certainly for experiments on suspended metal nanoparticles. Indeed, the extent to which light scattering can influence such optical experiments leads us to infer that many claims of a plasmonic effect could be misassigned

Galvanic Replacement Coupled to Seeded Growth as a Route for Shape-Controlled Synthesis of Plasmonic Nanorattles

Shape-controlled synthesis of metal nanoparticles (NPs) requires mechanistic understanding toward the development of modern nanoscience and nanotechnology. We demonstrate here an unconventional shape transformation of Au@Ag core–shell NPs (nanorods and nanocubes) into octahedral nanorattles via room-temperature galvanic replacement coupled with seeded growth. The corresponding morphological and chemical transformations were investigated in three dimensions, using state-of-the-art X-ray energy-dispersive spectroscopy (XEDS) tomography. The addition of a reducing agent (ascorbic acid) plays a key role in this unconventional mechanistic path, in which galvanic replacement is found to dominate initially when the shell is made of Ag, while seeded growth suppresses transmetalation when a composition of Au:Ag (∼60:40) is reached in the shell, as revealed by quantitative XEDS tomography. This work not only opens new avenues toward the shape control of hollow NPs beyond the morphology of sacrificial templates, but also expands our understanding of chemical transformations in nanoscale galvanic replacement reactions. The XEDS electron tomography study presented here can be generally applied to investigate a wide range of nanoscale morphological and chemical transformations