The behavior of metals across a broad frequency range from microwave to ultraviolet frequencies is of interest in plasmonics, nanophotonics, and metamaterials. Depending on the frequency, losses of collective excitations in metals can be predominantly classical resistive effects or Landau damping. In this context, we present first-principles calculations that capture all of the significant microscopic mechanisms underlying surface plasmon decay and predict the initial excited carrier distributions so generated. Specifically, we include ab initio predictions of phonon-assisted optical excitations in metals, which are critical to bridging the frequency range between resistive losses at low frequencies and direct interband transitions at high frequencies. In the commonly used plasmonic materials, gold, silver, copper, and aluminum, we find that resistive losses compete with phonon-assisted carrier generation below the interband threshold, but hot carrier generation via direct transitions dominates above threshold. Finally, we predict energy-dependent lifetimes and mean free paths of hot carriers, accounting for electron-electron and electron-phonon scattering, to provide insight toward transport of plasmonically generated carriers at the nanoscale.

Decay of surface plasmons to hot carriers finds a wide variety of applications in energy conversion, photocatalysis and photodetection. However, a detailed theoretical description of plasmonic hot-carrier generation in real materials has remained incomplete. Here we report predictions for the prompt distributions of excited ‘hot’ electrons and holes generated by plasmon decay, before inelastic relaxation, using a quantized plasmon model with detailed electronic structure. We find that carrier energy distributions are sensitive to the electronic band structure of the metal: gold and copper produce holes hotter than electrons by 1–2 eV, while silver and aluminium distribute energies more equitably between electrons and holes. Momentum-direction distributions for hot carriers are anisotropic, dominated by the plasmon polarization for aluminium and by the crystal orientation for noble metals. We show that in thin metallic films intraband transitions can alter the carrier distributions, producing hotter electrons in gold, but interband transitions remain dominant.

Nanoscale localization of electromagnetic fields near metallic nanostructures underpins the fundamentals and applications of plasmonics. The unavoidable energy loss from plasmon decay, initially seen as a detriment, has now expanded the scope of plasmonic applications to exploit the generated hot carriers. However, quantitative understanding of the spatial localization of these hot carriers, akin to electromagnetic near-field maps, has been elusive. Here we spatially map hot-electron-driven reduction chemistry with 15 nm resolution as a function of time and electromagnetic field polarization for different plasmonic nanostructures. We combine experiments employing a six-electron photo-recycling process that modify the terminal group of a self-assembled monolayer on plasmonic silver nanoantennas, with theoretical predictions from first-principles calculations of non-equilibrium hot-carrier transport in these systems. The resulting localization of reactive regions, determined by hot-carrier transport from high-field regions, paves the way for improving efficiency in hot-carrier extraction science and nanoscale regio-selective surface chemistry.