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Updated: Aug 4, 2025

Non-equilibrium Microwave Plasma for Efficient High Temperature Chemistry
Published on: August 1, 2017
Energy Transfer to Molecular Adsorbates by Transient Hot Electron Spillover
Mirko Vanzan1,2, Gabriel Gil3, Davide Castaldo1
1Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova, Italy.
Abstract:
Hot 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.
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