Abstract

In the last decades, theoretical and experimental studies of nanostructured materials have gathered the efforts of a big slice of the scientific community. Light–nanostructure interaction has been a preponderant research topic fueled by the interest in the plasmonic properties of metallic nanostructures. More recently, the study of plasmon-induced hot carrier generation has drawn the attention of scientists because of their potential application in optoelectronics, photovoltaics, and photocatalysis. In this contribution, we study the real-time electronic dynamics associated with the generation of hot carriers in silver and gold nanoparticles focusing on their energy distribution and atomic shell population/depopulation dynamics. Revisiting our previous results from the perspective of a generalized 2D correlation analysis paves the way to disentangle complex dynamic outcomes, such as the dissipation of the sp-band energy absorbed during plasmonic excitation. We show that this mechanism is founded on the dynamic cross-correlation between sp-band and d-band electronic populations. AB - In the last decades, theoretical and experimental studies of nanostructured materials have gathered the efforts of a big slice of the scientific community. Light–nanostructure interaction has been a preponderant research topic fueled by the interest in the plasmonic properties of metallic nanostructures. More recently, the study of plasmon-induced hot carrier generation has drawn the attention of scientists because of their potential application in optoelectronics, photovoltaics, and photocatalysis. In this contribution, we study the real-time electronic dynamics associated with the generation of hot carriers in silver and gold nanoparticles focusing on their energy distribution and atomic shell population/depopulation dynamics. Revisiting our previous results from the perspective of a generalized 2D correlation analysis paves the way to disentangle complex dynamic outcomes, such as the dissipation of the sp-band energy absorbed during plasmonic excitation. We show that this mechanism is founded on the dynamic cross-correlation between sp-band and d-band electronic populations.