Trigonal-to-monoclinic structural transition in TiSe$_2$ due to a combined condensation of $\mathbf{ \textit{q} = (\frac{1}{2},0,0)}$ and $\mathbf{(\frac{1}{2},0,\frac{1}{2})}$ phonon instabilities

Abstract

I present first principles calculations of the phonon dispersions of TiSe$_2$ in the $P\overline{3}c1$ phase, which is the currently accepted low-temperature structure of this material. They show weak instabilities in the acoustic branches in the out-of-plane direction, suggesting that this phase may not be the true ground state. To find the lowest energy structure, I study the energetics of all possible distorted structures corresponding to the isotropy subgroups of $P\overline{3}m1$ for the $M_1^-$ and $L_1^-$ phonon instabilities present in this high-temperature phase at $q = (\frac{1}{2},0,0)$ and $(\frac{1}{2},0,\frac{1}{2})$, respectively. I was able to stabilize 10 different structures that are lower in energy relative to the parent $P\overline{3}m1$ phase, including two monoclinic structures more energetically stable than the $P\overline{3}c1$ phase. The lowest energy structure has the space group $C2$ with the order parameter $M_1^- (a,0,0) + L_1^- (0,b,b)$. This structure lacks inversion symmetry, and its primitive unit cell has 12 atoms.