<br>通过 Aun(PH3)m 数据库研究金簇中磷化氢稳定的隐藏基态,ACS Nano

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通过 Aun(PH3)m 数据库研究金簇中磷化氢稳定的隐藏基态
ACS Nano ( IF 15.8 ) Pub Date : 2022-12-30 , DOI: 10.1021/acsnano.2c07223
Caitlin A McCandler _{1,

2} , Jakob C Dahl _{2,

3,

4} , Kristin A Persson _{1,

4}

Affiliation

纳米团簇由于其较大的表面积和独特的电子结构（可以通过成分、几何形状和化学性质进行定制）而成为用于催化和传感的有前途的材料。然而，将合成参数直接与结果相关联的关系是有限的。虽然之前的计算研究通过生成和计算合理结构的能量来绘制特定裸纳米团簇系统的势能面，但众所周知，环境离子和配体对最终的形状和尺寸有至关重要的影响。在这项工作中，磷化氢稳定金被视为测试系统，并对有和没有配体的团簇进行 DFT 计算，生成包含 Au _n (PH ₃ ) _m ( n ≤ 12) 的 >10000 结构的数据库。我们发现膦的连接会影响金纳米团簇的热力学稳定性、键合和电子结构，特别是使得在纯金系统中动态不稳定的“隐藏”基态团簇几何形状得以稳定。此外，磷化氢的添加引入了空间效应，导致 4-5 个 Au 原子（而不是多达 13-14 个 Au 原子）从平面结构转变为非平面结构，正如之前对裸簇的预测。这项工作强调了在预测纳米团簇形态和功能时考虑配体环境的重要性，这增加了复杂性并为可调谐性提供了丰富的机会。

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Phosphine-Stabilized Hidden Ground States in Gold Clusters Investigated via a Aun(PH3)m Database

Nanoclusters are promising materials for catalysis and sensing due to their large surface areas and unique electronic structures which can be tailored through composition, geometry, and chemistry. However, relationships correlating synthesis parameters directly to outcomes are limited. While previous computational studies have mapped the potential energy surface of specific systems of bare nanoclusters by generating and calculating the energies of reasonable structures, it is known that environmental ions and ligands crucially impact the final shape and size. In this work, phosphine-stabilized gold is considered as a test system and DFT calculations are performed for clusters with and without ligands, producing a database containing >10000 structures for Au_n(PH₃)_m (n ≤ 12). We find that the ligation of phosphines affects the thermodynamic stability, bonding, and electronic structure of Au nanoclusters, specifically such that “hidden” ground state cluster geometries are stabilized that are dynamically unstable in the pure gold system. Further, the addition of phosphine introduces steric effects that induce a transition from planar to nonplanar structures at 4–5 Au atoms rather than up to 13–14 Au atoms, as previously predicted for bare clusters. This work highlights the importance of considering the ligand environment in the prediction of nanocluster morphology and functionality, which adds complexity as well as a rich opportunity for tunability.

更新日期：2022-12-30

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