A new class of beryllium-boron clusters, beryllo-borospherene, is described herein theoretically. When beryllium is gradually added to the B12 motif, it undergoes drastic structural modifications. The global minimum of the Be4 B12 + cluster is an Archimedean beryllo-borospherene in a 2 A1 electronic ground state, composed of four boron triangles linked at each corner, resulting in a truncated tetrahedron with four B6 rings capped with four beryllium atoms. Beryllium forms strong bonding with the boron clusters through strong electrostatic and covalent interactions. For instance, the bonding between a beryllium atom and Be3 B12 unit is best described as a Be+ fragment in a 2 P excited state forming a strong and polarized electron-sharing bond with Be3 B12 , followed by several dative interactions by employing its vacant s, p, and very high-lying d orbitals. Counterintuitively, for an s-block element, the p orbitals of beryllium are the most crucial atomic orbitals for bonding rather than s orbitals.
Keywords: Ab Initio Calculations; Beryllium; Bonding; Boron; Doping.
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