Abstract
Atomically precise gold nanocluster based on linear assembly of repeating icosahedrons (clusters of clusters) is a unique type of linear nanostructure, which exhibits strong near-infrared absorption as their free electrons are confined in a one-dimensional quantum box. Little is known about the carrier dynamics in these nanoclusters, which limit their energy-related applications. Here, we reported the observation of exciton localization in triicosahedral Au(37) nanoclusters (0.5 nm in diameter and 1.6 nm in length) by measuring femtosecond and nanosecond carrier dynamics. Upon photoexcitation to S(1) electronic state, electrons in Au(37) undergo ∼100-ps localization from the two vertexes of three icosahedrons to one vertex, forming a long-lived S(1)* state. Such phenomenon is not observed in Au(25) (dimer) and Au(13) (monomer) consisting of two and one icosahedrons, respectively. We have further observed temperature dependence on the localization process, which proves it is thermally driven. Two excited-state vibration modes with frequencies of 20 and 70 cm(-1) observed in the kinetic traces are assigned to the axial and radial breathing modes, respectively. The electron localization is ascribed to the structural distortion of Au(37) in the excited state induced by the strong coherent vibrations. The observed electron localization phenomenon provides unique physical insight into one-dimensional gold nanoclusters and other nanostructures, which will advance their applications in solar-energy storage and conversion.