Density functional theory study of the structural, electronic, lattice dynamical, and thermodynamic properties of Li4SiO4and its capability for CO

The structural, electronic, lattice dynamical, optical, thermodynamic, and CO${}_{2}$ capture properties of monoclinic and triclinic phases of Li${}_{4}$SiO${}_{4}$ are investigated by combining density functional theory with phonon lattice dynamics calculations. We found that these two phases have some similarities in their bulk and thermodynamic properties. The calculated bulk modulus and the cohesive energies of these two phases are close to each other. Although both of them are insulators, the monoclinic phase of Li${}_{4}$SiO${}_{4}$ has a direct band gap of 5.24 eV while the triclinic Li${}_{4}$SiO${}_{4}$ phase has an indirect band gap of 4.98 eV. In both phases of Li${}_{4}$SiO${}_{4}$, the s orbital of O mainly contributes to the lower-energy second valence band (VB${}_{2}$) and the p orbitals contribute to the fist valence band (VB${}_{1}$) and the conduction bands (CBs). The s orbital of Si mainly contributes to the lower portions of the VB${}_{1}$ and VB${}_{2}$, and Si p orbitals mainly contribute to the higher portions of the VB${}_{1}$ and VB${}_{2}$. The s and p orbitals of Li contribute to both VBs and to CBs, and Li p orbitals have a higher contribution than the Li s orbital. There is possibly a phonon soft mode existing in triclinic \ensuremath{\gamma}-Li${}_{4}$SiO${}_{4}$; in the monoclinic Li${}_{4}$SiO${}_{4}$, there are three phonon soft modes, which correspond to the one type of Li disordered over a few sites. Their LO-TO splitting indicates that both phases of Li${}_{4}$SiO${}_{4}$ are polar anisotropic materials. The calculated infrared absorption spectra for LO and TO modes are different for these two phases of Li${}_{4}$SiO${}_{4}$. The calculated relationships of the chemical potential versus temperature and CO${}_{2}$ pressure for reaction of Li${}_{4}$SiO${}_{4}$ with CO${}_{2}$ shows that Li${}_{4}$SiO${}_{4}$ could be a good candidate for a high-temperature CO${}_{2}$ sorbent while used for postcombustion capture technology.