Abstract Metal-cluster surfaces present a wide variety of unique coordination environments. This complexity makes it difficult to manually probe the surface reactivity of such clusters. Here, we present a simple and automated method to systematically discover reaction pathways on cluster surfaces, based on the automated cluster surface scanning (ACSS) technique for mapping out potential energy surfaces. We showcase our method on 55-atom icosahedral Cu and Ag clusters, where we determine the activation energies of four elementary steps common in heterogeneous catalysis – hydrogen recombination (H* + H* → H2* + *), oxygen recombination (O* + O* → O2* + *), water formation (OH* + H* → H2O* + *), and CO oxidation (CO* + O* → CO2* + *) – with density functional theory calculations (DFT-PBE + D3). We show that the ACSS method requires significantly less human effort than the established manually performed climbing-image nudged elastic band (MP + CI-NEB) technique and locates transition states with comparable accuracy (root-mean-squared error of 0.10 eV) and similar computational cost. Rigorous sampling of the potential energy surface with the ACSS method allows one to locate all lowest-energy reaction pathways obtained via the MP+CI-NEB approach, as well as alternative pathways that one may have missed with the MP+CI-NEB approach due to the many possible pathways available on these clusters. The accuracy and efficiency afforded by the ACSS method could enable high-throughput exploration of the diverse reactivity of metal clusters.

中文翻译：

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一种用于探索金属簇表面反应路径的自动簇表面扫描方法

摘要 金属簇表面呈现出多种独特的配位环境。这种复杂性使得手动探测此类簇的表面反应性变得困难。在这里，我们基于用于绘制势能表面的自动簇表面扫描 (ACSS) 技术，提出了一种简单且自动化的方法来系统地发现簇表面上的反应途径。我们展示了我们在 55 个原子二十面体铜和银簇上的方法，我们确定了多相催化中常见的四个基本步骤的活化能 - 氢复合 (H* + H* → H2* + *)、氧复合 (O* + O* → O2* + *)、水形成 (OH* + H* → H2O* + *) 和 CO 氧化 (CO* + O* → CO2* + *) – 使用密度泛函理论计算 (DFT-PBE + D3)。我们表明，ACSS 方法所需的人力比已建立的手动执行的攀爬图像轻推弹性带 (MP + CI-NEB) 技术要少得多，并且以可比的精度（均方根误差为 0.10 eV）和类似的精度定位过渡态计算成本。使用 ACSS 方法对势能面进行严格采样，可以定位通过 MP+CI-NEB 方法获得的所有最低能量反应途径，以及由于 MP+CI-NEB 方法可能遗漏的替代途径到这些集群上可用的许多可能途径。ACSS 方法提供的准确性和效率可以实现对金属簇的不同反应性的高通量探索。