Vanzan, MirkoGil, GabrielCastaldo, DavideNordlander, PeterCorni, Stefano2023-04-252023-04-252023Vanzan, Mirko, Gil, Gabriel, Castaldo, Davide, et al.. "Energy Transfer to Molecular Adsorbates by Transient Hot Electron Spillover." <i>Nano Letters,</i> 23, no. 7 (2023) Amerian Chemical Society: 2719-2725. https://doi.org/10.1021/acs.nanolett.3c00013.https://hdl.handle.net/1911/114833Hot electron (HE) photocatalysis is one of the most intriguing fields of nanoscience, with a clear potential for technological impact. Despite much effort, the mechanisms of HE photocatalysis are not fully understood. Here we investigate a mechanism based on transient electron spillover on a molecule and subsequent energy release into vibrational modes. We use state-of-the-art real-time Time Dependent Density Functional Theory (rt-TDDFT), simulating the dynamics of a HE moving within linear chains of Ag or Au atoms, on which CO, N2, or H2O are adsorbed. We estimate the energy a HE can release into adsorbate vibrational modes and show that certain modes are selectively activated. The energy transfer strongly depends on the adsorbate, the metal, and the HE energy. Considering a cumulative effect from multiple HEs, we estimate this mechanism can transfer tenths of an eV to molecular vibrations and could play an important role in HE photocatalysis.engThis is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY).Journal articleacs-nanolett-3c00013https://doi.org/10.1021/acs.nanolett.3c00013