Abstract
Substrate-mediated mechanism of photochemical reactions on metals includes direct and/or plasmon-related excitation of electron–hole pairs in the bulk by photons and subsequent chemical transformation due to interaction of excited (hot) electrons (or holes) with the adsorbate. In nm-sized metal particles, the excited electrons are confined. We show in detail that this factor is beneficial for photochemistry under low-intensity steady-state conditions (linear regime) and also during intensive sub-ps laser pulses (non-linear regime). In both cases, the confinement may increase the contribution of secondary hot electrons to the photochemical conversion. In addition, in the non-linear regime the decrease of electron temperature after heating may be much slower than that on the surfaces of bulk samples and accordingly photochemical reactions may be more probable.
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