Recent studies on plasmon-catalysis postulate that the hot-electrons of plasmon-excited nanostructures may induce a non-thermal vibrational activation of metal-bound reactants. However, the postulate has not been fully validated at the level of molecular quantum states. We directly prove that such an activation occurs on plasmon-excited nanostructures: The Raman spectra of reactants undergoing a plasmon-catalyzed reaction reveal that a particular vibrational mode of the reactant is selectively excited, such that the reactants possess &gt;10 times more energy in the mode than is expected from the fully thermalized molecules. Furthermore, a significant portion of the excited-reactant is in vibrational overtone-states with energies exceeding 0.5 eV. Such mode-selective multi-quantum excitation, which is reproduced by the electron–molecule scattering model, validates the plasmon-catalysis mechanism and pave the way for controlling chemical reactions on metal surfaces.

Creation of vibrationally hot reactant by hot-carrier during a plasmon-catalyzed reaction

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