Minimizing lattice structures for Morse potential energy in two and three dimensions

Abstract

We investigate the local and global optimality of the triangular, square, simple cubic, face-centered-cubic (fcc) and body-centered-cubic (bcc) lattices and the hexagonal-close-packing (hcp) structure for a potential energy per point generated by a Morse potential with parameters (α, r0). In dimension 2 and for α large enough, the optimality of the triangular lattice is shown at fixed densities belonging to an explicit interval, using a method based on lattice theta function properties. Furthermore, this energy per point is numerically studied among all two-dimensional Bravais lattices with respect to their density. The behavior of the minimizer, when the density varies, matches with the one that has been already observed for the Lennard-Jones potential, confirming a conjecture we have previously stated for differences of completely monotone functions. Furthermore, in dimension 3, the local minimality of the cubic, fcc, and bcc lattices is checked, showing several interesting similarities with the Lennard-Jones potential case. We also show that the square, triangular, cubic, fcc, and bcc lattices are the only Bravais lattices in dimensions 2 and 3 being critical points of a large class of lattice energies (including the one studied in this paper) in some open intervals of densities as we observe for the Lennard-Jones and the Morse potential lattice energies. More surprisingly, in the Morse potential case, we numerically found a transition of the global minimizer from bcc, fcc to hcp, as α increases, that we partially and heuristically explain from the lattice theta function properties. Thus, it allows us to state a conjecture about the global minimizer of the Morse lattice energy with respect to the value of α. Finally, we compare the values of α found experimentally for metals and rare-gas crystals with the expected lattice ground-state structure given by our numerical investigation/conjecture. Only in a few cases does the known ground-state crystal structure match the minimizer we find for the expected value of α. Our conclusion is that the pairwise interaction model with Morse potential and fixed α is not adapted to describe metals and rare-gas crystals if we want to take into consideration that the lattice structure we find in nature is the ground-state of the associated potential energy.