Investigation of hardness in tetrahedrally bonded nonmolecularCO2solids by density-functional theory

Abstract

Stability and compressibility of several nonmolecular (polymeric) ${\mathrm{CO}}_{2}$ solids in structures analogous to those of ${\mathrm{SiO}}_{2}$ have been investigated with ab initio density-functional theory. Contrary to the recent experimental reports of a ``superhard'' high-pressure tridymite form of ${\mathrm{CO}}_{2},$ we find that metastable tetrahedrally bonded ${\mathrm{CO}}_{2}$ polymorphs, such as tridymite, cristobalite, and quartz, are relatively compressible, with bulk moduli K of only 1/2 to 1/3 of the reported experimental value. In addition, theory finds that the experimentally reported lattice parameters are not stable for ${\mathrm{CO}}_{2}$ ${P2}_{1}{2}_{1}{2}_{1}$ tridymite. Finally, none of the calculated x-ray spectra of the fully relaxed structures of ${\mathrm{CO}}_{2}$ polymorphs obtained from theory agrees with the experiments. The significant discrepancy between experiments and density-functional theory suggests that further studies on nonmolecular ${\mathrm{CO}}_{2}$ solids are necessary, and that the assumptions that density-functional theory can describe these materials correctly, or that the framework of the new nonmolecular ${\mathrm{CO}}_{2}$ solids contains only ${\mathrm{CO}}_{4}$ tetrahedra, must be re-examined.