Atomistic theory of hot carrier relaxation in large plasmonic nanoparticles

TL;DR

This paper develops an atomistic model to predict hot carrier populations in large plasmonic nanoparticles under continuous illumination, accounting for excitation and relaxation processes, with implications for photocatalysis and sensing.

Contribution

It introduces an atomistic approach to simulate hot carrier dynamics in large nanoparticles, considering material, size, and relaxation effects, which was previously challenging due to computational complexity.

Findings

Hot carrier populations vary with material and size.

Silver nanoparticles show larger temperature increases than gold.

Qualitative hot-carrier features are robust across relaxation models.

Abstract

Recently, there has been significant interest in harnessing hot carriers generated from the decay of localized surface plasmons in metallic nanoparticles for applications in photocatalysis, photovoltaics and sensing. In this work, we present an atomistic approach to predict the population of hot carriers under continuous wave illumination in large nanoparticles. For this, we solve the equation of motion of the density matrix taking into account both excitation of hot carriers as well as subsequent relaxation effects. We present results for spherical Au and Ag nanoparticles with up to $250,000$ atoms. We find that the population of highly energetic carriers depends both on the material and the nanoparticle size. We also study the increase in the electronic temperature upon illumination and find that Ag nanoparticles exhibit a much larger temperature increase than Au nanoparticles. Finally, we investigate the effect of using different models for the relaxation matrix but find that qualitative features of the hot-carrier population are robust.