Fa Wei, Dong Jinming
Group of Computational Condensed Matter Physics, National Laboratory of Solid State Microstructures, and Department of Physics, Nanjing University, Nanjing 210093, People's Republic of China.
J Chem Phys. 2008 Apr 14;128(14):144307. doi: 10.1063/1.2897917.
The structural and electronic properties of MAu16 (-) (M=Ag, Li, Na, and K) have been studied by the scalar relativistic all-electron density-functional calculations, in which particular attention is paid to the stability of the endohedral Au16 (-) cage doped by different dopant atoms. It is found that only the smaller atoms, such as Cu, Li, and Na, can be stably encapsulated in the Au16 (-) cage, while the addition of the larger Ag or K atom prefers to locate in the surface or outside of the cage, which is inconsistent with the previous hypothesis that the Au16 (-) cage could act as a container to hold an arbitrary heterometal atom. The stable endohedral Li@Au16 (-) and Na@Au16 (-) have a large energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital gap, indicating that they are chemically stable and may be used as potential building blocks for designing cluster-assembled materials.
通过标量相对论全电子密度泛函计算研究了MAu16 (-)（M = Ag、Li、Na和K）的结构和电子性质，其中特别关注了由不同掺杂原子掺杂的内包Au16 (-)笼的稳定性。结果发现，只有较小的原子，如Cu、Li和Na，能够稳定地封装在Au16 (-)笼中，而较大的Ag或K原子则更倾向于位于笼的表面或外部，这与之前认为Au16 (-)笼可以作为容纳任意异金属原子的容器的假设不一致。稳定的内包Li@Au16 (-)和Na@Au16 (-)在最高占据分子轨道和最低未占据分子轨道之间有较大的能隙，表明它们化学性质稳定，可能用作设计团簇组装材料的潜在构建单元。
