First principle calculation of physical properties of barium based chalcogenides BaM4S7 (M = Ga, Al); a DFT, DFT-D and hybrid functional HSE06 study

The electronic structure, elastic and optical properties have been calculated for the novel nonlinear optical (NLO) crystals BaQ4S7 (Q = Ga, Al) using plane wave pseudo-potential density functional theory (DFT) method as implemented in CASTEP and ABINIT codes. In this study we used both hybrid HSE06 and DFT-D functionals with GGA approximation. These NLO compounds, which belong to the mm2 point group, are particularly interesting because of their transparency in the mid-infrared region and wide energy band gap. We present results for electronic structure, elastic tensor coefficients, refractive indices and second order nonlinear optical susceptibilities. The calculated energy band gap and frequency dependent refractive indices as well as the NLO coefficients of BaGa4S7 are in good agreement with the experimental values. With no reported theoretical or experimental energy band gap and optical properties of BaAl4S7, we present for the first time its electronic structure and above mentioned optical coefficients. This compound has higher direct band gap with 3.74 eV, better optical birefringence and second-order NLO coefficients than most NLO compounds. The second-order NLO coefficients for BaAl4S7 have been calculated as d31 = 3.15 pm/V, d31 = 2.20 pm/V, d33 = −6.31 pm/V.