Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun 130023, People's Republic of China.
J Phys Chem A. 2011 Mar 17;115(10):2041-6. doi: 10.1021/jp110417z. Epub 2011 Feb 21.
Superalkalies with low ionization potentials (IPs) can exhibit behaviors reminiscent of alkali atoms and hence be considered as potential building blocks for the assembly of novel nanostructured materials. A new series of binuclear superalkali cations M(2)Li(2k+1)(+) (M = F, O, N, C) has been studied using ab initio methods. The structural features of such cations are found to be related to the central atoms. In the preferred structures of F(2)Li(3)(+), O(2)Li(5)(+), and N(2)Li(7)(+), two central atoms are bridged by lithium atoms. While in the global minima of C(2)Li(9)(+), two central carbon atoms directly link each other and the C-C unit extends to the surface of the whole system. These M(2)Li(2k+1)(+) species exhibit very low vertical electron affinities of 2.74-4.61 eV at the OVGF/6-311+G(3df) level and hence should be classified as superalkali cations.
具有低电离势 (IP) 的超碱金属可以表现出类似于碱金属原子的行为，因此可以被认为是组装新型纳米结构材料的潜在构建块。我们使用从头算方法研究了一系列新的双核超碱金属阳离子 M(2)Li(2k+1)(+) (M = F, O, N, C)。发现这些阳离子的结构特征与中心原子有关。在 F(2)Li(3)(+)、O(2)Li(5)(+) 和 N(2)Li(7)(+) 的优先结构中，两个中心原子通过锂原子桥接。而在 C(2)Li(9)(+) 的全局最小值中，两个中心碳原子直接相互连接，C-C 单元延伸到整个系统的表面。这些 M(2)Li(2k+1)(+) 物种在 OVGF/6-311+G(3df) 水平下表现出非常低的垂直电子亲合能，为 2.74-4.61 eV，因此应被归类为超碱金属阳离子。
