Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 106, Taiwan.
J Phys Condens Matter. 2013 Mar 27;25(12):125305. doi: 10.1088/0953-8984/25/12/125305. Epub 2013 Feb 28.
The 13-atom metal clusters of fcc elements (Al, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au) were studied by density functional theory calculations. The global minima were searched for by the ab initio random structure searching method. In addition to some new lowest-energy structures for Pd13 and Au13, we found that the effective coordination numbers of the lowest-energy clusters would increase with the ratio of the dimer-to-bulk bond length. This correlation, together with the electronic structures of the lowest-energy clusters, divides the 13-atom clusters of these fcc elements into two groups (except for Au13, which prefers a two-dimensional structure due to the relativistic effect). Compact-like clusters that are composed exclusively of triangular motifs are preferred for elements without d-electrons (Al) or with (nearly) filled d-band electrons (Ni, Pd, Cu, Ag). Non-compact clusters composed mainly of square motifs connected by some triangular motifs (Rh, Ir, Pt) are favored for elements with unfilled d-band electrons.
采用密度泛函理论计算研究了面心立方(fcc)元素(Al、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au)的 13 原子金属团簇。通过从头算随机结构搜索方法搜索全局最小能量结构。除了 Pd13 和 Au13 的一些新的最低能量结构外，我们还发现最低能量团簇的有效配位数会随着二聚体-体相键长比的增加而增加。这种相关性，以及最低能量团簇的电子结构，将这些 fcc 元素的 13 原子团簇分为两组(除了 Au13，由于相对论效应，Au13 更喜欢二维结构)。不含 d 电子的元素(Al)或 d 带电子几乎填满的元素(Ni、Pd、Cu、Ag)优先形成仅由三角图案组成的紧凑样团簇。主要由通过一些三角图案连接的正方形图案组成的非紧凑团簇(Rh、Ir、Pt)则优先于未填满 d 带电子的元素。
