Comparison of features arising in phonon spectra of crystals belonging to the argyrodite family for various combinations of orbits filled with Ag (Cu) atoms

Abstract

The paper is devoted to model phonon spectra calculations of argyrodite family crystals, namely: Ag7GeSe5I and Cu7GeSe5I (Ag7SiS5I and Cu7SiS5I). The specificity of the crystalline structure of these crystals is realization of variable partial populating different crystallographic orbits with Cu, I and Ag atoms (in 24 (g) and 48 (h) Positions Multiplicity, Wyckoff letter, Site symmetry of the space group F 43m), which are associated with high superionic conductivity in crystals of this family. Compared in this paper are model phonon spectra calculated with account of three different configurations of orbital populations with Cu and Ag atoms (6 + 1, 5 + 2 and 4 + 3), by choosing the same lattice model for the unit cell and the set of force constants of each crystal. The calculations were performed by finding the eigenvalues of the generalized dynamic matrix perturbed by the modulation function of the mass defect obtained in the concept over spatial symmetry. It is shown that the phonon spectra do not undergo significant qualitative changes, which can serve as indirect evidence of the possibility to realize the jumping mechanism of super-ionic conductivity in these crystals in the high-temperature phase.