Heterogeneous catalysis is of paramount importance in chemistry and energy applications. Catalysts that couple light energy into chemical reactions in a directed, orbital-specific manner would greatly reduce the energy input requirements of chemical transformations, revolutionizing catalysis-driven chemistry. Here we report the room temperature dissociation of H(2) on gold nanoparticles using visible light. Surface plasmons excited in the Au nanoparticle decay into hot electrons with energies between the vacuum level and the work function of the metal. In this transient state, hot electrons can transfer into a Feshbach resonance of an H(2) molecule adsorbed on the Au nanoparticle surface, triggering dissociation. We probe this process by detecting the formation of HD molecules from the dissociations of H(2) and D(2) and investigate the effect of Au nanoparticle size and wavelength of incident light on the rate of HD formation. This work opens a new pathway for controlling chemical reactions on metallic catalysts.

Clusters of plasmonic nanoparticles and nanostructures support Fano resonances. Here we show that this spectral feature, produced by the interference between bright and dark modes of the nanoparticle cluster, is strongly dependent upon both geometry and local dielectric environment. This permits a highly sensitive tunability of the Fano dip in both wavelength and amplitude by varying cluster dimensions, geometry, and relative size of the individual nanocluster components. Plasmonic nanoclusters show an unprecedented sensitivity to dielectric environment with a local surface plasmon resonance figure of merit of 5.7, the highest yet reported for localized surface plasmon resonance sensing in a finite nanostructure.

Studying the plasmonic properties of metallic nanoparticles at the individual nanostructure level is critical to our understanding of nanoscale metallic systems. Here we show how the presence of a nearby dielectric substrate modifies the energies of the plasmon modes of a metallic nanoparticle. The adjacent dielectric lifts the degeneracy of the dipole plasmon modes oriented parallel and perpendicular to the substrate, introducing a significant energy splitting that depends strongly on the permittivity of the substrate. This energy splitting can easily be misinterpreted as an anomalously broadened plasmon line shape for excitation of an individual nanoparticle with unpolarized light.

Plasmonic nanoparticle pairs known as "dimers" embody a simple system for generating intense nanoscale fields for surface enhanced spectroscopies and for developing an understanding of coupled plasmons. Individual nanoshell dimers in directly adjacent pairs and touching geometries show dramatically different plasmonic properties. At close distances, hybridized plasmon modes appear whose energies depend extremely sensitively on the presence of a small number of molecules in the interparticle junction. When touching, a new plasmon mode arising from charge transfer oscillations emerges. The extreme modification of the overall optical response due to minute changes in very reduced volumes opens up new approaches for ultrasensitive molecular sensing and spectroscopy.