The nonmonotonous shift of quantum plasmon resonance and plasmon-enhanced photocatalytic activity of gold nanoparticles.

The surface plasmon resonance (SPR) of metal nanoparticles exhibits quantum behaviors as the size decreases owing to the transitions of quantized conduction electrons, but most studies are limited to the monotonous SPR blue-shift caused by off-resonant transitions. Here, we demonstrate the nonmonotonous SPR red-shift caused by resonant electron transitions and photocatalytic activity enhanced by the quantum plasmon resonance of colloidal gold nanoparticles. A maximal SPR wavelength and the largest photocatalytic activity are observed in the quantum regime for the first time for the gold nanoparticles with a diameter of 3.6 nm. Theoretical analysis based on a quantum-corrected model reveals the evolution of SPR with quantized electron transitions and well explains the nonmonotonous size-dependencies of the SPR wavelength and absorption efficiency. These findings have profound implications for the understanding of the quantum nature of the SPR of metal nanoparticles and their applications in areas ranging from photophysics to photochemistry.