Atomistic simulation of hot carrier generation in large plasmonic nanoparticles

Energetic or “hot” carriers in metallic nanoparticles are generated from the decay of the localized surface plasmon via the Landau damping mechanism and can be harnessed for applications in photocatalysis or sensing. A detailed understanding of hot-carrier properties and their dependence on the nanoparticle size, composition, environment and shape is needed to optimize devices. However, standard electronic structure methods, such as those based on first-principles density-functional theory [1], cannot be applied to nanoparticles of experimentally relevant sizes. To address this challenge, we use a recently developed approach that combines an atomistic tight- binding description of the nanoparticles with a Chebyshev decomposition of Fermi's golden rule [2] in order to calculate the rate of hot carrier generation. This opens up the possibility of simulating nanoparticles with millions of atoms. We will present results for hot-carrier generation rates of gold nanoparticles of different shapes including cubes, octahedra and dodecahedra and discuss their potential for the photocatalytic reduction of CO2 into high-value chemicals.

[1] N. Asadi-Aghbolaghi, J. Phys. Chem. C 124, 14, 7946–7955 (2020)

[2] H. Jin et al, PRX Energy 1, 013006 (2022)