Tuning photoelectron dynamic behavior of thiolate-protected MAu24 nanoclusters via heteroatom substitution. Issue 10 (30th August 2022)

• Record Type: Journal Article
• Authors: Yu, Xueke; Sun, Yuanze; Xu, Wen-wu; Fan, Junyu; Gao, Junfeng; Jiang, Xue; Su, Yan; Zhao, Jijun
• Is Part Of: Nanoscale horizons. Volume 7:Issue 10(2022)
• Page Start: 1192
• Page End: 1200
• Publication Date: 2022-08-30
• Subjects: Nanoscience -- Periodicals; Nanotechnology -- Periodicals; 620.505
• DOI: 10.1039/d2nh00281g
• Languages: English
• ISSNs: 2055-6756

Abstract

Abstract : Heteroatom substitution of MAu24 (SR)18 nanoclusters enables precise tuning of their physicochemical properties at the single-atom level, including the electronic structures, vibrational properties, and photocarrier dynamic behavior. Abstract : 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.