Pressure Effect of the Vibrational and Thermodynamic Properties of Chalcopyrite-Type Compound AgGaS(2): A First-Principles Investigation

To explore the structural, vibrational, and thermodynamic properties of the chalcopyrite-type compound AgGaS(2) under pressure, we applied hydrostatic pressure to the relaxed compound based on the first principles calculation and quasi-harmonic approximation. The structural parameters, including lattice constants and bond lengths decrease monotonically with the increasing pressure. The phonon dispersion curves under various pressures reveal the structural phase transition of chalcopyrite-type compound AgGaS(2) at about 4 GPa. The intrinsic mechanism of thermal conductivity for the chalcopyrite-type compound AgGaS(2) has been shown with phonon anharmonicity. The frequencies of the optical phonons at the center point Γ of the first Brillouin zone were calculated with the longitudinal optical–transverse optical (LO–TO) splitting mode. The dependence of the frequencies of the optical phonons on the pressure provides the information for the Raman spectroscopic study under high pressure. The pressure dependence of the Grüneisen parameters indicates that the instability of chalcopyrite-type compound AgGaS(2) is associated with the softening of the acoustic phonon modes at around the center point Γ. The thermal conductivity for chalcopyrite-type compound AgGaS(2) could be reduced by applying external pressure. The various thermodynamic properties, such as the Helmholtz free energy, entropy, and heat capacity, at different temperatures and pressures were discussed and analyzed based on the phonon properties.