Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, China.
Phys Chem Chem Phys. 2010 May 21;12(19):5156-65. doi: 10.1039/b923003c. Epub 2010 Apr 1.
The geometrical structures, relative stabilities, and electronic properties of small bare gold clusters Au(n)(lambda) and bimetallic complexes of bare metal clusters with one copper atom Au(n-1)Cu(lambda) (charge lambda = 0, +1, -1; 2 < or = n < or = 9) have been systematically investigated by means of first-principles density functional calculations at the B3LYP level. The results show that the most stable isomers have a planar structure and resemble pure gold clusters in shape, and no three-dimensional isomers were obtained for neutral and anionic doped gold clusters. However, the geometries of Au(n-1)Cu(+) are found to undergo a structural change from two dimensional to three dimensional when the cluster contains 7 atoms. The calculated dissociation energy and second difference energy as a function of the cluster size exhibit a pronounced even-odd alternation phenomenon. Ionization potentials and electron detachment energies (both vertical and adiabatic) of Au(n)(lambda) and Au(n-1)Cu(lambda) clusters are discussed and compared with available experimental results. A good agreement between experimental and theoretical results suggests good prediction of the lowest energy structures for all clusters calculated in the present study.
采用第一性原理密度泛函理论 B3LYP 方法，系统地研究了裸露金原子簇 Au(n)(lambda)和单铜原子掺杂的裸露金属原子簇 Au(n-1)Cu(lambda)（电荷 lambda = 0, +1, -1；2 <= n <= 9）的几何结构、相对稳定性和电子性质。结果表明，最稳定的异构体具有平面结构，形状类似于纯金原子簇，未得到中性和阴离子掺杂金原子簇的三维异构体。然而，当簇包含 7 个原子时，Au(n-1)Cu(+)的几何形状从二维变为三维。计算所得的离解能和二阶差分能随团簇尺寸的变化表现出明显的奇偶交替现象。讨论了 Au(n)(lambda)和 Au(n-1)Cu(lambda)团簇的电离势和电子离域能（垂直和绝热），并与可用的实验结果进行了比较。实验结果与理论结果的良好一致性表明，本研究中计算的所有团簇的最低能量结构具有良好的预测性。
