Crystal Structure of the High-Pressure Phase of Solid CO2

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Science  21 Jan 1994:
Vol. 263, Issue 5145, pp. 356-358
DOI: 10.1126/science.263.5145.356


X-ray diffraction study of solid CO2 at room temperature has shown that the powder pattern of the high-pressure phase, which supersedes the low-pressure cubic Pa3 phase at about 10 gigapascals, is consistently interpreted in terms of an orthorhombic Cmca structure. The orthorhombic cell at 11.8 gigapascals has dimensions of 4.330 ± 0.015, 4.657 ± 0.005, 5.963 ± 0.009 angstroms for its a, b, and c faces, respectively, and a volume of 120.3 ± 0.5 cubic angstroms. Four molecules contained in the unit cell are located at the base-centered positions with their molecular axes inclined at about 52° with respect to the crystallographic c axis. The volume change associated with the Pa3-Cmca transition is close to zero. The structural dimensions obtained for the high-pressure crystalline phase of CO2 are of great importance for a theoretical understanding of the role of intermolecular interactions, including quadrupole-quadrupole interactions, in molecular condensation.