SP3-Hybridization Feature of Ag4 Superatom in Superatomic Molecules†
SP3-Hybridization Feature of Ag4 Superatom in Superatomic Molecules†
复制标题
DOI：
10.1063/1674-0068/28/cjcp1505105
复制
发表时间：
2015-09
影响因子：
1
通讯作者：
Lijuan Yan;Longjiu Cheng;Jin-long Yang
中科院分区：
文献类型：
--
作者：
Lijuan Yan;Longjiu Cheng;Jin-long Yang
与原子类似，超原子可以作为组成分子和材料的基石。为了证明这一想法，讨论了利用四面体Ag4簇形成一系列超原子分子Ag4X4 （X=H, Li, Na， K, Cu, Ag， Au和F， Cl, Br）的可能性。基于超价键模型，四面体Ag4簇可以看作是一个具有4个电子的超原子，可以模拟sp3杂化C原子。将具有代表性的超原子分子Ag4X4 （X=Au, Cl）与相应的简单分子CX4 （X=H, Cl）进行比较，发现它们在化学键模式和分子轨道（MOs）方面具有明显的相似性。能量计算预测Ag4超原子可以与所有相关配体结合。此外，超原子分子的最大已占据轨道和最低未占据轨道的大间隙（HOMO-LUMO间隙）和高芳构性增强了超原子分子的稳定性。我们的研究可能会在用超原子组装材料方面找到应用。
Analogous to atoms, superatoms can be used as building blocks to compose molecules and materials. To demonstrate this idea, the possibility of using tetrahedral Ag4 cluster to form a series of superatomic molecules Ag4X4 (X=H, Li, Na, K, Cu, Ag, Au and F, Cl, Br) is discussed. Based on the super valence bond model, a tetrahedral Ag4 cluster can be viewed as a 4-electron superatom, which can mimic a sp3 hybridization C atom. By comparison of the representative superatomic molecules Ag4X4 (X=Au, Cl) with the corresponding simple molecules CX4 (X=H, Cl), the similarities in terms of chemical bonding patterns and molecular orbitals (MOs) are conspicuous. Energy calculations predict that the Ag4 superatom can bind with all the involved ligands. Furthermore, the stabilities of superatomic molecules are enhanced by the large gaps of the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO gaps) and high aromaticity. Our studies may find applications in assembling materials with superatoms.