Hangzhou Institute of Advanced Studies, Zhejiang Normal University, 1108 Gengwen Road, Hangzhou 311231, China.
Key Laboratory of Excited-State Materials of Zhejiang Province, Department of Chemistry, Zhejiang University, Hangzhou 310058, China.
J Phys Chem Lett. 2023 Jun 29;14(25):5818-5826. doi: 10.1021/acs.jpclett.3c01533. Epub 2023 Jun 20.
The structures of large cadmium selenide clusters are poorly understood due to the presence of challenging long-range Coulombic interactions and a vast number of possible structures. In this study, we present an unbiased fuzzy global optimization method that incorporates atom-pair hopping, ultrafast shape recognition, and adaptive temperatures within a directed Monte Carlo framework to enhance the search efficiency of binary clusters. Using this method and first-principles calculations, we successfully obtain the lowest-energy structures of (CdSe) clusters with 5 ≤ ≤ 80. The putative global minima reported in the literature have been obtained. The binding energy per atom tends to decrease with cluster size. Our results show that the stable structures evolve from rings to stacked rings, cages, nanotubes, cage-wurtzite, cage-core, and finally wurtzite structures, enabling us to reveal a systematic structural evolution for the growth of cadmium selenide clusters without ligands.
由于存在具有挑战性的长程库仑相互作用和大量可能的结构，大型硒化镉团簇的结构仍未被充分了解。在这项研究中，我们提出了一种无偏的模糊全局优化方法，该方法将原子对跳跃、超快形状识别和自适应温度纳入定向蒙特卡罗框架内，以提高二元团簇的搜索效率。使用这种方法和第一性原理计算，我们成功地获得了（CdSe）簇的最低能量结构，其中 5≤ ≤80。已经得到了文献中报道的假定全局最小值。每个原子的结合能随着团簇尺寸的增加而减小。我们的结果表明，稳定的结构从环到堆叠环、笼、纳米管、笼-纤锌矿、笼核、最终到纤锌矿结构演变，使我们能够揭示没有配体的情况下硒化镉团簇生长的系统结构演化。
