Persistence and eventual demise of oxygen molecules at terapascal pressures

TL;DR

This study uses density-functional-theory to explore how solid oxygen's structure and electronic properties evolve under extremely high pressures up to several terapascals, revealing phase transitions from molecular to polymeric and metallic states.

Contribution

It provides detailed predictions of oxygen's structural transformations and electronic behavior at pressures up to 9.5 TPa, a regime largely unexplored experimentally.

Findings

Molecular oxygen persists up to 1.9 TPa before transforming.

Oxygen becomes semiconducting with a band gap of about 3.0 eV at 1.9 TPa.

Oxygen adopts metallic structures at pressures above 3.0 TPa.

Abstract

Computational searches for structures of solid oxygen under pressures in the multi TPa range have been carried out using density-functional-theory methods. We find that molecular oxygen persists to about 1.9 TPa at which it transforms into a semiconducting square spiral-like polymeric structure (I41/acd) with a band gap of about 3.0 eV. Solid oxygen forms a metallic zig-zag chain-like structure (Cmcm) at about 3.0 TPa, but the chains in each layer gradually merge as the pressure is increased and a structure of Fmmm symmetry forms at about 9.5 TPa in which each atom has four nearest neighbors. The superconducting properties of molecular oxygen do not vary much with compression, although the structure becomes more symmetric. The electronic properties of oxygen have a complex evolution with pressure, swapping between insulating, semiconducting and metallic.