  Metal nanoparticles are attractive for plasmon-enhanced generation of hot
carriers, which may be harnessed in photochemical reactions. In this work, we
analyze the coherent femtosecond dynamics of photon absorption, plasmon
formation, and subsequent hot-carrier generation through plasmon dephasing
using first-principles simulations. We predict the energetic and spatial
hot-carrier distributions in small metal nanoparticles and show that the
distribution of hot electrons is very sensitive to the local structure. Our
results show that surface sites exhibit enhanced hot-electron generation in
comparison to the bulk of the nanoparticle. While the details of the
distribution depend on particle size and shape, as a general trend
lower-coordinated surface sites such as corners, edges, and {100} facets
exhibit a higher proportion of hot electrons than higher-coordinated surface
sites such as {111} facets or the core sites. The present results thereby
demonstrate how hot carriers could be tailored by careful design of
atomic-scale structures in nanoscale systems.
