Hydrocarbons under pressure: phase diagrams and surprising new compounds in the C-H system

• Published in: arXiv.org
• Main Authors: Naumova, Anastasia S, Lepeshkin, Sergey V, Oganov, Artem R
• Format: Paper
• Language: English
• Published: Ithaca Cornell University Library, arXiv.org 05.04.2019
• Subjects: Energy storage; Hydrocarbons; Methane; Organic chemistry; Phase diagrams; Polyethylenes; Potential energy; Predictions; Stability

Understanding the high-pressure behavior of C-H system is of great importance due to its key role in organic, bio-, petroleum and planetary chemistry. We have performed a systematic investigation of the pressure-composition phase diagram of the C-H system at pressures up to 400 GPa using evolutionary structure prediction coupled with ab initio calculations and discovered that only saturated hydrocarbons are thermodynamically stable. Several stable methane-hydrogen co crystals are predicted: 2CH4 * H2, earlier obtained experimentally, is predicted to have I4/m space group and 2-90 GPa stability range at 0 K, and two new thermodynamically stable compounds 2CH4 * 7H2 (P-3m1 space group) and CH4 * 9H2 (Cm space group), as potential energy storage materials. P21/c phase of methane is predicted to be stable at pressures < 8 GPa; bulk graphane (CH) was shown to be thermodynamically stable at 7-18 and 18-50 GPa and 0 K in the P-3m and Cmca phases, respectively; polyethylene is shown to have a narrow field of stability. We report the p-T-x phase diagram of the C-H system and p-T phase diagram of CH4.