Synthesis, Structure, and Electrical Properties of the Single Crystal Ba₈Cu₁₆As₃₀

Single crystals of clathrate-I Ba₈Cu₁₆As₃₀ have been synthesized and their structure and electronic properties determined using synchrotron-based X-ray diffraction and first-principles calculations. The structure is confirmed to be Pm3̅n (No. 223), with lattice parameter a = 10.4563(3) Å, and defined by a tetrahedrally bonded network of As and Cu that forms two distinct coordination polyhedra, with Ba residing inside these polyhedra. All crystallographic positions are fully occupied with no vacancies or superstructure with the Cu atoms, while occupying all framework sites in the network, exhibiting a preference for the 6c site. Agreement between the experimental and theoretically predicted structures was achieved after accounting for spin–orbit coupling. Our calculated Fermi surface, electron localization, and charge transfer, as well as a comparison with the results for elemental As₄₆, provide insight into the fundamental properties of this clathrate-I material.