Insights from Experiment and Theory on Peculiarities of the Electronic Structure and Optical Properties of the Tl(2)HgGeSe(4) Crystal

[Image: see text] Tl(2)HgGeSe(4) crystal was successfully, for the first time, synthesized by the Bridgman–Stockbarger technology, and its electronic structure and peculiarities of optical constants were investigated using both experimental and theoretical techniques. The present X-ray photoelectron spectroscopy measurements show that the Tl(2)HgGeSe(4) crystal reveals small moisture sensitivity at ambient conditions and that the essential covalent constituent of the chemical bonding characterizes it. The latter suggestion was supported theoretically by ab initio calculations. The present experiments feature that the Tl(2)HgGeSe(4) crystal is a high-resistance semiconductor with a specific electrical conductivity of σ ∼ 10(–8) Ω(–1) cm(–1) (at 300 K). The crystal is characterized by p-type electroconductivity with an indirect energy band gap of 1.28 eV at room temperature. It was established that a good agreement with the experiments could be obtained when performing first-principles calculations using the modified Becke–Johnson functional as refined by Tran–Blaha with additional involvement in the calculating procedure of the Hubbard amendment parameter U and the impact of spin–orbit coupling (TB-mBJ + U + SO model). Under such a theoretical model, we have determined that the energy band gap of the Tl(2)HgGeSe(4) crystal is equal to 1.114 eV, and this band gap is indirect in nature. The optical constants of Tl(2)HgGeSe(4) are calculated based on the TB-mBJ + U + SO model.