Ab initio study of the electronic and optical properties of sillimanite (Al2SiO5) crystal

Ab initio calculations based on the density functional theory (DFT) are used to investigate the electronic and optical properties of sillimanite. The geometrical parameters of the unit cell, which contain 32 atoms, have been fully optimized and are in good agreement with the experimental data. The electronic structure shows that sillimanite has an indirect band gap of 5.18 eV. The complex dielectric function and optical constants, such as extinction coefficient, refractive index, reflectivity and energy-loss spectrum, are calculated. The optical properties of sillimanite are discussed based on the band structure calculations. It is shown that the O-2p states and Al-3s, Si-3s states play the major role in optical transitions as initial and final states, respectively.

► The electronic and optical properties of sillimanite are investigated by first-principles calculations. ► The electronic structure of sillimanite crystal has an indirect band gap of 5.18 eV. ► The O-2p states and Al-3s, Si-3s states play the major role in optical transitions as initial and final states, respectively. ► The pure sillimanite crystal does not absorb radiation in the visible range.