Heteroatom substitution of gold nanoclusters permits exact tuning of their physicochemical properties at single-atom degree, which has significance affect on the functions associated to excited states together with photovoltaic, photocatalysis and photo-luminescence. To this finish, understanding the impact of metallic change on the constructions, digital properties and photoexcited dynamic conduct of nanoclusters is crucial. Combining density useful principle with time-domain nonadiabatic molecular dynamics simulation, herein we explored the impact of metallic substitute on digital and vibrational properties in addition to excited-state dynamics of ligand-protected MAu24(SR)18 (M = Pd, Pt, Cd, and Hg) nanoclusters. At atomistic degree, we elucidate scorching provider leisure and recombination dynamic conduct with numerous doping atoms. Such distinct excited-state conduct of MAu24(SR)18 nanoclusters is attributed to totally different power gaps and electron–phonon coupling between the donor and acceptor power ranges, owing to the perturbation of nanocluster by single international atom. The precise phonon modes concerned in excited-state dynamics have been recognized, that are related to the MAu12 core and ligand rings. This time-dependent excited-state dynamic examine fills the hole between construction/composition and excited-state dynamic conduct of MAu24(SR)18 nanoclusters, which might stimulate the exploration of their functions involving photoenergy storage and conversion.