A solid–solid phase transition in carbon dioxide at high pressures and intermediate temperatures

• Published in: Nature communications Vol. 4; no. 1; p. 2647
• Main Authors: Li, Jinjin, Sode, Olaseni, Voth, Gregory A., Hirata, So
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 2013; Nature Publishing Group
• Subjects: 119/118; 140/133; 639/301/1034; 639/638/440/951; Humanities and Social Sciences; multidisciplinary; Science; Science (multidisciplinary)
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/ncomms3647

Despite its terrestrial abundance and astrochemical significance, many aspects of the phase diagram of solid carbon dioxide remain uncertain or unknown. The observed transition pressures from cubic to orthorhombic phase range widely from 2.5 GPa at 80 K to above 18 GPa at room temperature. The vibrational Raman bands that appear at higher pressure and serve as a decisive proof of the existence of the orthorhombic phase have never been assigned. Here we introduce a general ab initio computational method that can predict the Gibbs free energies and thus phase diagrams of molecular crystals. Using this with second-order Møller—Plesset perturbation theory, we obtain the transition pressure of 13 GPa at 0 K with small temperature dependence, which is in line with many experiments. We also computationally reproduce the vibrational Raman bands and explain the pressure dependence of the structure parameters and Raman band positions of both phases quantitatively. It is desirable for scientists to be able to predict the structures, spectra and phase diagrams of molecular crystals using ab initio computation. Li et al . demonstrate such an approach, which is able to determine the phase behaviour of solid carbon dioxide at a range of pressures and temperatures.