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Ligand–core interaction in ligand-protected Ag25(XR)18 (X = S, Se, Te) superatoms and evaluation of the anchor atom role via relativistic DFT calculations
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2022-06-24 , DOI: 10.1039/d2cp01058e
Alvaro Muñoz-Castro 1
Affiliation  

The isostructural and isoelectronic silver [Ag25(SR)18] (R = ligand) cluster, similar to [Au25(SR)18] gold clusters, allows for further understanding of the fundamental similarities between Au and Ag at the ultrasmall nanoscale (<2 nm), featuring an eight cluster electron (8-ce) M13 core. Our results indicate a less favorable protecting-layer to core interaction, leading to a more symmetrical Ag13 core owing to a less tight ligand shell. The stabilizing embrace of Ag13 is of an electrostatic character, with bonding contributions occupying the formally unoccupied superatomic shells, given by 1D, 2S, and 2F, indicating their role as acceptor core orbitals to provide further core–ligand bonding upon the formation of the cluster. The optical properties exhibit a red-shift for the first 1P → 1D peak along the [Ag25(XMe)18] series, which is in contrast with the blue-shift observed for the gold counterpart, by replacing the S-anchor atom with Se and Te. Moreover, the S1 → S0 emission exhibits a red-shift. Thus, the role of the anchor atom is to modify the bonding and optical features of the [Ag25(XMe)18] species, affording fine-tuning of the molecular behavior.

中文翻译:

配体保护的 Ag25(XR)18 (X = S, Se, Te) 超原子中的配体-核心相互作用和通过相对论 DFT 计算评估锚原子作用

等结构和等电子的银 [Ag 25 (SR) 18 ] - (R = 配体) 簇,类似于 [Au 25 (SR) 18 ] -金簇,允许进一步了解 Au 和 Ag 在超小尺寸上的基本相似性纳米级(<2 nm),具有八簇电子(8-ce)M 13核心。我们的结果表明,保护层与核心的相互作用不太有利,由于配体壳不太紧密,导致 Ag 13核心更加对称。Ag 13的稳定拥抱具有静电特性,键合贡献占据了由 1D、2S 和 2F 给出的形式上未被占据的超原子壳层,表明它们作为受体核心轨道的作用是在簇形成时提供进一步的核配体键合。沿着[Ag 25 (XMe) 18 ] -系列的第一个 1P → 1D 峰的光学性质表现出红移,这与通过替换 S 锚原子观察到的金对应物的蓝移相反与 Se 和 Te。此外,S 1 → S 0发射表现出红移。因此,锚原子的作用是改变 [Ag 25 (XMe) 18 ]的键合和光学特征-物种,提供分子行为的微调。
更新日期:2022-06-24
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