Nonradiative Dynamics of [Au 25 (SCH 3 ) 18 ] − Nanoclusters: Many-Body versus Single-Particle Excited State Dynamics

作者：Junping Xie, Wei Li, Yong Pei · 发表于：The Journal of Physical Chemistry Letters · 年份：2025 · DOI：10.1021/acs.jpclett.5c02926 · 被引用次数：5 · 研究领域：Nanocluster Synthesis and Applications、Advanced Nanomaterials in Catalysis、Gold and Silver Nanoparticles Synthesis and Applications

Thiolate-protected gold nanoclusters (Au NCs) have attracted significant attention for their potential in photovoltaics, photocatalysis, and photoluminescence. Realizing the full potential of these applications requires a detailed understanding of the photoinduced excited-state dynamics. Here, we investigate the nonradiative relaxation dynamics of photoexcited carriers in the prototypical [Au 25 (SCH 3 ) 18 ] − nanocluster using ab initio nonadiabatic molecular dynamics (NAMD) simulations, incorporating both single-particle (SP) and many-body (MB) treatments of electronic excited states. Our results reveal distinct and contrasting roles of MB effects in internal conversion and nonradiative recombination processes. In particular, MB effects accelerate the relaxation of high energy excited states to the subpicosecond time scale by enhancing nonadiabatic couplings relative to SP description. In contrast, MB treatment slows the electron–hole recombination of the lowest-lying excited states (431.8 ps vs 136.5 ps in SP), owing to the weakened nonadiabatic couplings with ground state and enhanced uphill transitions among degenerate lowest-lying excited states. Relaxation from higher-energy states involves both core-to-semiring and core-to-core transitions, whereas charge recombination predominantly proceeds via core-to-core pathways. Low-frequency vibrational modes associated with the Au(core)–Au(core) and Au(core)–Au(ring) interactions couple strongly to the nonradiative relaxation...