Hot-carrier generation from surface plasmon decay has found many applications in many branches of physics, chemical, materials, and energy science. Especially, recent efforts indicated that the hot-carriers generated from plasmon decay in nanoparticles could transfer to attached molecules and drive the photochemistry of impossible in previous thought. In this work, we explored the atomic-scale mechanism of plasmonic hot-carrier mediated chemical reaction exampled by H<sub>2</sub> splitting by employing time-dependent density functional calculations theory and non-adiabatic molecular dynamics. The numerical simulation demonstrates that the anti-bonding state of the attached molecule is found to be slightly higher than the Fermi level and the potential energy surface of the excited state of the adsorbed molecule keeps the anti-bonding feature. Consequently, the hot-carriers generated from the nanoparticle can transfer to the anti-bonding state of the attached molecule and drive the photochemical reaction. Then, we also found chemical reaction is tunable if the molecule is placed in the center of the plasmonic dimer. The reaction rate can be either suppressed or enhanced depending on the geometry. In general, symmetry broken is essential to enhance the reaction rate. Thus, our work demonstrates the possibility of tunable photochemistry via plasmonic hot-carriers.

Plasmonic hot-carriers mediated tunable photochemical reactions: A non-adiabatic molecular dynamics study of H<sub>2</sub> splitting

256th National Meeting (2018)

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Plasmonic hot-carriers mediated tunable photochemical reactions: A non-adiabatic molecular dynamics study of H2 splitting

Plasmonic hot-carriers mediated tunable photochemical reactions: A non-adiabatic molecular dynamics study of H₂ splitting