We report a comprehensive study of aqueous halide adsorption on nanoparticles of gold and palladium that addresses several limitations hampering the use of atomistic modeling as a tool for understanding and improving wet-chemical synthesis and related applications. A combination of thermodynamic modeling with density functional theory (DFT) calculations and experimental data is used to predict equilibrium shapes of halide-covered nanoparticles as a function of the chemical environment. To ensure realistic and experimentally relevant results, we account for solvent effects and include a large set of vicinal surfaces, several adsorbate coverages, as well as decahedral particles. While the observed stabilization is not significant enough to result in thermodynamic stability of anisotropic shapes such as nanocubes, nonuniformity in the halide coverage indicates the possibility of obtaining such shapes as kinetic products. With regard to technical challenges, we show that inclusion of surface-solvent interactions leads to qualitative changes in the predicted shape. Furthermore, accounting for nonlocal interactions on the functional level yields a more accurate description of surface systems.

中文翻译：

---

卤化物在纳米粒子生长中作为形状导向剂的功效的计算评估

我们报告了金和钯的纳米粒子上卤化物水溶液吸附的综合研究，该研究解决了一些限制原子模型作为理解和改进湿化学合成及相关应用的工具的局限性的问题。热力学建模与密度泛函理论（DFT）计算和实验数据的结合可用于预测卤化物覆盖的纳米颗粒的平衡形状，该形状取决于化学环境。为了确保获得与实验相关的现实结果，我们考虑了溶剂的影响，并包括大量的邻面，数个被吸附物以及十面体颗粒。虽然观察到的稳定性不足以导致各向异性形状（例如纳米立方体）的热力学稳定性显着降低，卤化物覆盖范围的不均匀性表明有可能获得诸如动力学产物的形状。关于技术挑战，我们表明包含表面溶剂相互作用会导致预测形状发生质变。此外，在功能级别上考虑非局部相互作用会产生对表面系统的更准确描述。