Free-Energy Landscape and Isomerization Rates of Au 4 Clusters at Finite Temperatures
Free-Energy Landscape and Isomerization Rates of Au 4 Clusters at Finite Temperatures
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有限温度下 Au 4 团簇的自由能景观和异构化速率
DOI：
10.1021/acs.jpca.2c02732
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Whitmer, Jonathan K.
中科院分区：
文献类型：
--
作者：
Shi, Jiale;Huang, Shanghui;Gygi, François;Whitmer, Jonathan K.
在金属纳米粒子中，原子位置的几何形状控制粒子的电子能带结构、极化率和催化性质。分析结构性质是一个复杂的问题;由于热涨落，组装的团簇的结构随时都在变化。基于光谱学或衍射的常规结构分析不能精确地确定瞬时结构，并且只能提供平均结构。分子模拟提供了一个机会，检查组装和金属簇的演变，作为首选的组件和构象可以很容易地可视化和探索。在这里，我们利用自适应偏置力算法应用于第一性原理分子动力学演示探索一个相对简单的系统，它允许一个全面的研究小金属簇Au 4在中性和带电配置。我们的模拟工作提供了对这些团簇的动力学结构的定量理解，这对于金属团簇上的单中心催化反应具有重要意义，并为更复杂的纯金属和合金团簇的动力学性质的详细定量理解提供了起点。
In metallic nanoparticles, the geometry of atomic positions controls the particle’s electronic band structure, polarizability, and catalytic properties. Analyzing the structural properties is a complex problem; the structure of an assembled cluster changes from moment to moment due to thermal fluctuations. Conventional structural analyses based on spectroscopy or diffraction cannot determine the instantaneous structure exactly and can merely provide an averaged structure. Molecular simulations offer an opportunity to examine the assembly and evolution of metallic clusters, as the preferred assemblies and conformations can easily be visualized and explored. Here, we utilize the adaptive biasing force algorithm applied to first-principles molecular dynamics to demonstrate the exploration of a relatively simple system, which permits a comprehensive study of the small metal cluster Au4in both neutral and charged configurations. Our simulation work offers a quantitative understanding of these clusters’ dynamic structure, which is significant for single-site catalytic reactions on metal clusters and provides a starting point for a detailed quantitative understanding of more complex pure metal and alloy clusters’ dynamic properties.