AAuAl (A = Ca, Sc, and Ti): Peierls Distortion, Atomic Coloring, and Structural Competition

Using density functional theory, the crystal structure variation of AAuAl (A = Ca, Sc, and Ti) from orthorhombic Co 2 Si-type to distorted hexagonal Fe 2 P-type and then Ni 2 In-type structures is shown to correlate with their electronic structures and valence electron counts, sizes of the active metals A, and site preferences for Au and Al atoms, which are arranged to maximize Au-Al nearest neighbor contacts. An evaluation of chemical pressure imposed by the varying A metals using total energy vs volume calculations indicates that larger unit cell volumes favor the orthorhombic structure, whereas smaller volumes favor the hexagonal structures. The electronic origin of the Mg 2 Ga-type crystal structure of ScAuAl, refined as a distorted Fe 2 P-type supercell doubled along the c-axis, indicates a Peierls-type distortion mechanism of the Au chains along the c-axis.