Electronic band structure of LiInSe2: A first-principles study using the Tran-Blaha density functional and GW approximation

• The structural and electronic properties of LiInSe2 compound are reported.
• The performance of different exchange-correlation functionals is analyzed.
• The band gap is predicted to be 2.95 eV within GW approximation.
• The band gap pressure coefficient of LiInSe2 is larger than those of CuInSe2 and AgInSe2.

Using first-principles theoretical techniques within density functional theory and many-body perturbation theory we investigated the structural and electronic properties of two LiInSe2 crystal modifications, orthorhombic (β-NaFeO2-type) and tetragonal (CuFeS2-type), focusing on the interband transitions and band gaps. It is found that the Tran-Blaha (TB09) functional predicts LiInSe2 to be a direct-gap semiconductor with a significantly larger band gap as compared with that from common local-density and gradient-corrected functionals. The most accurate values of the fundamental energy gaps are calculated within quasiparticle GW approximation and found to be 2.95 eV for the orthorhombic phase and 2.85 eV for the tetragonal one, with equal pressure coefficients of 63 meV/GPa. Our theoretical results eliminate the uncertainty in the band gap of LiInSe2. Moreover, the data obtained define the upper limit of the band gap of solid solutions (Cu,Li)InSe2 and (Ag,Li)InSe2, which can be of interest for applications in optoelectronics.