Tuning photoelectron dynamic behavior of thiolate-protected MAu₂₄ nanoclusters via heteroatom substitution

Heteroatom substitution of gold nanoclusters enables precise tuning of their physicochemical properties at the single-atom level, which has a significant impact on the applications related to excited states including photovoltaics, photocatalysis and photo-luminescence. To this end, understanding the effect of metal exchange on the structures, electronic properties and photoexcited dynamic behavior of nanoclusters is imperative. Combining density functional theory with time-domain nonadiabatic molecular dynamics simulations, herein we explored the effect of metal replacement on the electronic and vibrational properties as well as excited-state dynamics of ligand-protected MAu₂₄(SR)₁₈ (M = Pd, Pt, Cd, and Hg) nanoclusters. At the atomistic level, we elucidate hot carrier relaxation and recombination dynamic behavior with various doping atoms. Such distinct excited-state behavior of MAu₂₄(SR)₁₈ nanoclusters is attributed to different energy gaps and electron-phonon coupling between the donor and acceptor energy levels, owing to the perturbation of nanoclusters by a single foreign atom. The specific phonon modes involved in excited-state dynamics have been identified, which are associated with the MAu₁₂ core and ligand rings. This time-dependent excited-state dynamic study fills the gap between structure/composition and excited-state dynamic behavior of MAu₂₄(SR)₁₈ nanoclusters, which would stimulate the exploration of their applications in photoenergy storage and conversion.