title: Plasmonic hot electron transport drives nano-localized chemistry.
abstract: 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.
authors.affiliation: The Blackett Laboratory, Department of Physics, Imperial College London, London SW7 2AZ, UK.
authors.forename: Emiliano
authors.initials: E
authors.lastname: Cortés
authors.affiliation: Physical Chemistry I, Department of Chemistry and Center for Nanointegration Duisburg-Essen (CENIDE), University of Duisburg-Essen, Universitätsstrasse 5, 45141 Essen, Germany.|Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China.
authors.forename: Wei
authors.initials: W
authors.lastname: Xie
authors.affiliation: The Blackett Laboratory, Department of Physics, Imperial College London, London SW7 2AZ, UK.
authors.forename: Javier
authors.initials: J
authors.lastname: Cambiasso
authors.affiliation: Institute of Astronomy, Cambridge University, Cambridge CB3 0HA, UK.|Faculty of Arts and Sciences, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: Adam S
authors.initials: AS
authors.lastname: Jermyn
authors.affiliation: Department of Materials Science and Engineering, Rensselaer Polytechnic Institute, 110 8th street, Troy, New York 12180, USA.
authors.forename: Ravishankar
authors.identifier: 0000-0002-0625-4592
authors.initials: R
authors.lastname: Sundararaman
authors.affiliation: Faculty of Arts and Sciences, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: Prineha
authors.initials: P
authors.lastname: Narang
authors.affiliation: Physical Chemistry I, Department of Chemistry and Center for Nanointegration Duisburg-Essen (CENIDE), University of Duisburg-Essen, Universitätsstrasse 5, 45141 Essen, Germany.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Schlücker
authors.affiliation: The Blackett Laboratory, Department of Physics, Imperial College London, London SW7 2AZ, UK.
authors.forename: Stefan A
authors.initials: SA
authors.lastname: Maier