Clear mechanistic insights into excited state dynamics in thiolate-protected gold nanoclusters are vital for understanding the origin of the photocatalytic enhancement via metal nanoparticles in the visible region. Extensive experimental… Click to show full abstract
Clear mechanistic insights into excited state dynamics in thiolate-protected gold nanoclusters are vital for understanding the origin of the photocatalytic enhancement via metal nanoparticles in the visible region. Extensive experimental studies on the [Au25(SR)18]−1 thiolate-protected gold nanocluster nonradiative relaxation dynamics reported very distinct time constants which span from the femtosecond to nanosecond scale. In this work, the nonradiative excited state relaxations of the [Au25(SH)18]−1 cluster are investigated theoretically to characterize the electron relaxation dynamics. The core and higher excited states lying in the energy range 0.00–2.20 eV are investigated using time-dependent density functional theory (TD-DFT). The quantum dynamics of these states is studied using a surface hopping method with decoherence correction, augmented with a real-time approach to DFT. Population transfer from the S1 state to the ground state occurs on the several hundred picoseconds time scale. Relaxation b...
               
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