Distinct vibrational signatures and complex phase behavior in metallic oxygen

Evidence for metallization in dense oxygen has been reported for over 30 years [Desgreniers et al., J. Phys. Chem. 94, 1117 (1990)] at a now routinely accessible 95 GPa [Shimizu et al., Nature 393, 767 (1998)]. However, despite the longevity of this result and the technological advances since, the nature of the metallic phase remains poorly constrained [Akahama et al., Phys. Rev. Lett. 74, 4690 (1995); Goncharov et al., Phys. Rev. B 68, 224108 (2003); Ma, Phys. Rev. B 76, 064101 (2007); and Weck et al., Phys. Rev. Lett. 102, 255503 (2009)]. In this work, through Raman spectroscopy, we report the distinct vibrational characteristics of metallic ζ-O2 from 85 to 225 GPa. In comparison with numerical simulations, we find reasonable agreement with the C2/m candidate structure up to about 150 GPa. At higher pressures, the C2/m structure is found to be unstable and incompatible with experimental observations. Alternative candidate structures, C2/c and Ci, with only two molecules in the primitive unit cell, are found to be stable and more compatible with measurements above 175 GPa, indicative of the dissociation of (O2)4 units. Further, we report and discuss a strong hysteresis and metastability with the precursory phase ϵ-O2. These findings will reinvigorate experimental and theoretical work into the dense oxygen system, which will have importance for oxygen-bearing chemistry, prevalent in the deep Earth, as well as fundamental physics.