Solid oxygen


Solid oxygen forms at normal atmospheric pressure at a temperature below 54.36 K. Solid oxygen O2, like liquid oxygen, is a clear substance with a light sky-blue color caused by absorption in the red part of the visible light spectrum.
Oxygen molecules have attracted attention because of the relationship between the molecular magnetization and crystal structures, electronic structures, and superconductivity. Oxygen is the only simple diatomic molecule to carry a magnetic moment. This makes solid oxygen particularly interesting, as it is considered a "spin-controlled" crystal that displays antiferromagnetic magnetic order in the low temperature phases. The magnetic properties of oxygen have been studied extensively. At very high pressures, solid oxygen changes from an insulating to a metallic state; and at very low temperatures, it even transforms to a superconducting state. Structural investigations of solid oxygen began in the 1920s and, at present, six distinct crystallographic phases are established unambiguously.
The density of solid oxygen ranges from 21 cm3/mol in the α-phase, to 23.5 cm3/mol in the γ-phase.

Phases

Six different phases of solid oxygen are known to exist:
  1. α-phase: light blue forms at 1 atm, below 23.8 K, monoclinic crystal structure.
  2. β-phase: faint blue to pink forms at 1 atm, below 43.8 K, rhombohedral crystal structure,.
  3. γ-phase: faint blue forms at 1 atm, below 54.36 K, cubic crystal structure.
  4. δ-phase: orange forms at room temperature at a pressure of 9 GPa
  5. ε-phase: dark-red to black forms at room temperature at pressures greater than 10 GPa
  6. ζ-phase: metallic forms at pressures greater than 96 GPa
It has been known that oxygen is solidified into a state called the β-phase at room temperature by applying pressure, and with further increasing pressure, the β-phase undergoes phase transitions to the δ-phase at 9 GPa and the ε-phase at 10 GPa; and, due to the increase in molecular interactions, the color of the β-phase changes to pink, orange, then red, and the red color further darkens to black with increasing pressure. It was found that a metallic ζ-phase appears at 96 GPa when ε-phase oxygen is further compressed.

Red oxygen

As the pressure of oxygen at room temperature is increased through 10 GPa, it undergoes a dramatic phase transition to a different allotrope. Its volume decreases significantly, and it changes color from sky-blue to deep red. This ε-phase was discovered in 1979, but the structure has been unclear. Based on its infrared absorption spectrum, researchers assumed in 1999 that this phase consists of molecules in a crystal lattice. However, in 2006, it was shown by X-ray crystallography that this stable phase known as ε oxygen or red oxygen is in fact. No one predicted the structure theoretically: a rhomboid cluster consisting of four molecules.
Ball-and-stick model of O8
Part of the crystal structure of ε-oxygen

In this phase it exhibits a dark-red color, very strong infrared absorption, and a magnetic collapse. It is also stable over a very large pressure domain and has been the subject of numerous X-ray diffraction, spectroscopic and theoretical studies. It has been shown to have a monoclinic C2/m symmetry and its infrared absorption behaviour was attributed to the association of oxygen molecules into larger units.
A ζ-phase appears at 96 GPa when ε-phase oxygen is further compressed. This phase was discovered in 1990 by pressurizing oxygen to 132 GPa. The ζ-phase with metallic cluster exhibits superconductivity at pressures over 100 GPa and a temperature below 0.6 K.