Cortés, EmilianoXie, WeiCambiasso, JavierJermyn, Adam S.Sundararaman, RavishankarNarang, PrinehaSchlücker, SebastianMaier, Stefan A.2017-05-012017Cortés, Emiliano, Wei Xie, Javier Cambiasso, Adam S. Jermyn, Ravishankar Sundararaman, Prineha Narang, Sebastian Schlücker, and Stefan A. Maier. 2017. “Plasmonic hot electron transport drives nano-localized chemistry.” Nature Communications 8 (1): 14880. doi:10.1038/ncomms14880. http://dx.doi.org/10.1038/ncomms14880.http://nrs.harvard.edu/urn-3:HUL.InstRepos:32630691Nanoscale 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.en-USJournal Article2017-05-0110.1038/ncomms14880