Pressure-Dependent hcp-to-fcc Phase Transition Path Derived from Exact Lattice Summations over Inverse Power Law Potentials

We investigate the phase transition between hexagonal close-packed (hcp) and face-centered cubic (fcc) structures along the Burgers-Bain transformation path at pressures up to several hundred gigapascals. We consider a hierarchy of interatomic potentials, from (n,m)-Lennard-Jones potentials to extended Lennard-Jones two-body interactions in terms of inverse-power expansions and the Axilrod-Teller-Muto three-body term, alongside density functional theory (DFT) calculations for solid argon. For inverse-power potentials, free energies are evaluated through exact lattice sums and efficient integral representations based on generalizations of the Epstein zeta function to anisotropic interaction kernels, followed by lattice-parameter optimization. This methodology enables an accurate determination of the pressure-dependent Burgers-Bain minimum-energy path and the associated activation barrier for the phase transition. The transformation exhibits pronounced symmetry breaking connecting the Burgers and Bain paths, a feature confirmed by DFT calculations. At high pressure, the hcp-to-fcc activation barrier increases approximately linearly with pressure, owing to the dominant pressure-volume contribution. Including entropy and anharmonic effects yields excellent agreement with experimental temperature-dependent volumes up to the melting point. DFT results also highlight the increasing importance of many-body interactions under compression. Whereas two-body potentials predict that the path passes through the body-centered cubic (bcc) structure only at very high pressures, DFT generally predicts a pathway that bypasses bcc. The Axilrod-Teller-Muto term slightly reduces this discrepancy. Furthermore, DFT performs better at high pressures, where dispersion forces become less important.

Recommended citation: Maltby, T. W., Robles-Navarro, A., Hartlaub, J. K., Buchheit, A. A., Wilhelmsen, Ø., Hammer, M., & Schwerdtfeger, P. (2026). "Pressure-Dependent hcp-to-fcc Phase Transition Path Derived from Exact Lattice Summations over Inverse Power Law Potentials." arXiv preprint arXiv:2610.22855. DOI: 10.48550/arXiv.2610.22855