LAUSR

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...