Electronic, vibrational, and thermodynamic properties of metacinnabar β-HgS, HgSe, and HgTe

We report ab initio calculations of the electronic band structure and the phonon dispersion relations of the zincblende-type mercury chalcogenides (beta-HgS, HgSe, and HgTe). The latter have been used to evaluate the temperature dependence of the specific heat, which has been compared with experimental data. The electronic band structure of these materials has been confirmed to have an inverted direct gap of the alpha-tin type, which makes HgSe and HgTe semimetallic. For beta-HgS, however, our calculations predict a negative spin-orbit splitting that restores semiconducting properties to the material in spite of the inverted gap. We have calculated the spin-orbit induced linear terms in k, which appear at the Gamma(8) valence bands. We have also investigated the pressure dependence of the crystal structure and the phonons.