B63: The Most Stable Bilayer Structure with Dual Aromaticity.

ABSTRACT

The emergence of a bilayer B48 cluster, which has been both theoretically predicted and experimentally observed, as well as the recent experimental synthesis of bilayer borophene sheets on Ag and Cu surfaces, has generated tremendous curiosity in the bilayer structures of boron clusters. However, the connection between bilayer boron cluster and bilayer borophene remains unknown. By combining a genetic algorithm and density functional theory calculations, a global search for the low-energy structures of the B63 cluster was conducted, revealing that the Cs bilayer structure with three interlayer B-B bonds is the most stable bilayer structure. This structure was further examined in terms of its structural stability, chemical bonding, and aromaticity. Interestingly, the interlayer bonds induce strong electronegativity and robust aromaticity. Furthermore, the dual aromaticity stems from diatropic currents originating from virtual translational transitions for both σ and π electrons. This unprecedent bilayer boron cluster is anticipated to enrich the concept of dual aromaticity and serve as a potential precursor for bilayer borophene.