Li₂B₁₂ and Li₃B₁₂: Prediction of the Smallest Tubular and Cage‐like Boron Structures

Abstract

Abstract An intriguing structural transition from the quasi‐planar form of B 12 cluster upon the interaction with lithium atoms is reported. High‐level computations show that the lowest energy structures of LiB 12 , Li 2 B 12 , and Li 3 B 12 have quasi‐planar ( C s ), tubular ( D 6 d ), and cage‐like ( C s ) geometries, respectively. The energetic cost of distorting the B 12 quasi‐planar fragment is overcompensated by an enhanced electrostatic interaction between the Li cations and the tubular or cage‐like B 12 fragments, which is the main reason of such drastic structural changes, resulting in the smallest tubular (Li 2 B 12 ) and cage‐like (Li 3 B 12 ) boron structures reported to date.