Structures of group-15 elemental solids from an effective boundary theory

Abstract

We present an effective description for the crystal structures of pnictogen elemental solids. In these materials, each atom contains three valence electrons in $p$ orbitals. They are shared between neighbouring atoms to form valence bonds. We propose a trivalent network model on the simple cubic lattice. As a generalization of a dimer model, we impose a constraint that three dimers must touch every site. We argue that intra-orbital Coulomb repulsion prohibits the formation of two adjacent, parallel dimers. This leads to a tripod-like local configuration at every site. More importantly, it forces every line of the cubic lattice to have alternating dimers and blanks. There is no dynamics as dimers cannot be locally rearranged. A bulk-boundary mapping emerges whereby bonds in the interior are fully described by Ising variables on three bounding planes -- a simple example of holography that may be realized in real materials. To describe the energetics of bonding, we formulate a minimal model in terms of boundary Ising spins. Symmetries reduce the problem to that of three identical, independent, two-dimensional Ising models. An antiferromagnetic Ising-ground-state corresponds to the A7 structure seen in antimony and grey arsenic. An antiferromagnetic phase within a bilayer describes the structure of phosphorene. By stacking such bilayers, we obtain the A17 structure of black phosphorus. The stripe phase of the Ising models describes the cubic gauche structure of nitrogen. As a testable signature, we demonstrate that single impurities will induce long-ranged domain walls.