Peierls transition in sodium under high pressure: a first-principles study.

We have used first-principles calculations to investigate the electronic structure of the new oP8 phase of sodium which was experimentally reported recently (Gregoryanz et al 2008 Science 320 1054). Our results show the transition from I-43d to oP8 structure, which happens at room temperature, can also happen at 0 K. The I-43d structure will change to the oP8 structure at about 155 GPa and 0 K, rather than the CsIV structure at 190 GPa and 0 K, as the previous studies (Neaton et al 2001 Phys. Rev. Lett. 86 2830) predicted. It is also found that the oP8 structure forms a new nonequilateral triangle Na(3) structure and mainly distributes charge accumulation in the voids of the structure, rather than within the Na(3) triangles. Electronic density of states analysis shows that the oP8 structure opens a deeper pseudogap close to the Fermi level through symmetry breaking of the structure compared with that of the I-43d structure. Together with its unusual charge density distribution, it is found that the Peierls mechanism works for the transition to the oP8 structure. Differing from previous results about the Peierls mechanism of light alkali metals, the unit which produces a one-dimensional charge density wave is the Na(3) cluster instead of the pairing mechanism.