High-Angular-Momentum Orbitals and Superatomic Characteristics of Boron-Nitrogen Cages

The functional structures at the nanoscale containing high-angular-momentum (HAM) electrons possess wide potential applications. However, HAM electrons generally exist in high-Z elements, while the related materials are difficult to obtain through either mining or synthesis. Therefore, it is significant to design new materials building blocks to mimic the electronic properties of high-Z elements. In this study, a series of cage structures formed by light elements of boron and nitrogen (BN) have been proven to present superatomic properties. Especially, the superatomic molecular orbitals of the BN cage are found, all containing orbitals occupied by HAM electrons, for example, f, g, and h. Their electronic configurations can be represented as 1S(2)1P(6)1D(10)1F(14)2S(2)2P(6)1G(18)2D(10)1H(10)2F(6), 1S(2)1P(6)1D(10)1F(14)1G(18)2S(2)2P(6)1H(22)2D(10)2F(14), and 1S(2)1P(6)1D(10)1F(14)1G(18)1H(22)2S(2)2P(6)2D(10)2F(14) for B12N12, B16N16, and B28N28 structures, respectively. These findings open up a prospect of using abundant light elements to form superatomic structures with HAM electronic characteristics and are of significance for the development of functional materials and devices.