Electronic and optical properties of the thio-apatites phases Ba$_5$(VS$_{\alpha}$O$_{\beta}$)$_3$X [X=Cl, F, Br, I]: impact of multiple anionic substitution

Abstract

A systematic study of the electronic structure and optical properties of the thio-apatites Ba$_5$(VS$_{\alpha}$O$_{\beta}$)$_3$X (X= Cl, F, Br, I) is carried out through first principles density functional theory simulations. The band gap and properties evolution from fluorine to iodine on fixed O/S ratios, as well as by substituting sulfur (S) for oxygen (O) are discussed. The reduction of the band gap by raising valence band energy levels, with an increasing S/O ratio can also be further modulated by the type of halide in the channels of the structure, thus promoting fine tuning of the band gap region. Defect states also play a crucial role in band gap modulation. Furthermore, the examination of the band edges properties in Ba$_5$(VS$_{\alpha}$O$_{\beta}$)$_3$X compounds suggests they can be potential photocatalysts candidates for the water splitting reaction, with reduced band gaps enabling efficient light-driven reactions, particularly in Ba$_5$(VS$_{\alpha}$O$_{\beta}$)$_3$I. Optical investigations reveal that sulfur doping induces optical anisotropy, enhancing light absorption and offering tailored optical behaviour. These results provide new insights for the design of functional materials in the broad family of apatites.