Beryllium, an s-block element, forms an aromatic network of delocalized Be–Be π bonds in alloys ZrBe
2 and HfBe
2. This gives rise to stacked [Be
2]
4− layers with tetravalent cations in between. The [Be
2]
4− sublattice is isoelectronic and isostructural to graphite, as well as the [B]
−2 sublattice in MgB
2, and it bears identical manifestations of π bonding in its electronic band structure. These come in the form of degeneracies at K and H in the Brillouin zone, separated in energy as the result of interlayer orbital interactions. Zr and Hf use their valence d orbitals to form bonds with the layers, leading to nearly identical band structures. Like MgB
2, ZrBe
2 and HfBe
2 are computed to be phonon-mediated superconductors at ambient pressures, with respective critical temperatures of 11.4 K and 8.8 K. The coupling strength between phonons and free electrons is very similar, so that the difference in critical temperatures is controlled by the mass of constituent interlayer ions.
