Binary compounds of boron and beryllium: a rich structural arena with space for predictions

We explore ground-state structures and stoichiometries of the Be-B system in the static limit, with Be atom concentrations of 20 % or greater, and from P = 1 atm up to 320 GPa. At P = 1 atm, predictions are offered for several known compounds, the structures of which have not yet been determined experimentally. Specifically, at 1 atm, we predict a structure of R3m symmetry for the compound Be2B3, seen experimentally at high temperatures, which contains interesting BeBBBBe rods; and for the compound BeB4 we calculate metastability with respect to the elements with a structure similar to MgB4, which is quickly replaced as the pressure is elevated by a Cmcm structure that features 6- and 4-membered rings in B cages, with Be interstitials. For another high-temperature compound, Be2B, we confirm the CaF2 structure, but find a competitive and actually slightly more stable ground-state structure of C2/m symmetry that features B2 pairs. In the case of BeB2, a material for which the stoichiometry has been the subject of debate, we have a clear prediction of a stable F43m structure at P=1 atm. It has a diamondoid structure that is based on cubic (lower P) or hexagonal (higher P) diamond networks of B, but with Be in the interstices. This Zintl structure is a semiconductor at low and intermediate pressures. At higher pressures, BeB2 dominates the phase diagram. In general, the Zintl-Klemm concept of effective electron transfer from the more electropositive ion and bond formation among the resulting anions has proven useful in analyzing the structural preferences of many compositions in the Be-B system at P=1 atm and at elevated pressures. An unusual feature of this binary system is that the 1:1 BeB stoichiometry never appears to reach stability in the static limit, although it comes close, as does Be17B12. Also stable at high pressures are stoichiometries BeB3, BeB4, and Be5B2.