Pressure-Induced Structural Phase Transition and Superconductivity in NaSn₅

The structural and electronic properties of the tin-rich compound NaSn₅ were investigated under pressures of up to 10 GPa on the basis of the evolutionary algorithm (EA) technique coupled with first-principles total energy calculations. Upon compression, the known metallic tetragonal P4̅2₁m phase transforms into a metallic hexagonal P6/mmm phase at 1.85 GPa accompanied by an unusual change in the existing form of Sn atoms. The P6/mmm phase can be interpreted as a quasi-layered sandwich structure with two Sn layers and one sodium layer. The presence of softening phonon modes and the existence of Fermi pockets together with the obvious Fermi surface nesting indicate a strong electron–phonon coupling (EPC) and thus potential superconductivity in the P6/mmm phase. The strong EPC in the P6/mmm phase is mainly attributed to the phonons from Sn1 atoms together with electrons from the Sn1 p_y and Sn1 p_z states. The calculated superconducting critical temperature T_c of the P6/mmm phase is 5.91 K at 1.85 GPa. This study provides a new clue for designing intercalated compounds with superconductivity.