• DOI:10.1126/science.1244989
• Corpus ID: 15298372

Unexpected Stable Stoichiometries of Sodium Chlorides

@article{Zhang2013UnexpectedSS,
  title={Unexpected Stable Stoichiometries of Sodium Chlorides},
  author={Weiwei Zhang and Artem R. Oganov and Alexander F. Goncharov and Qiang Zhu and Salah Eddine Boulfelfel and Andriy O. Lyakhov and Elissaios Stavrou and Maddury Somayazulu and Vitali B. Prakapenka and Zuzana Kon{\^o}pkov{\'a}},
  journal={Science},
  year={2013},
  volume={342},
  pages={1502 - 1505}
}

• Weiwei Zhang, A. Oganov, +7 authors Z. Konôpková
• Published 15 November 2012
• Materials Science
• Science

Salt to Squeeze Simple table salt, NaCl, is the only known stable phase of Na and Cl at ambient conditions. Previous attempts to understand its structure and chemical properties under pressure and at high temperatures revealed phase and bonding transitions, while keeping the balance of one Na to one Cl. Using crystal structure prediction algorithms, Zhang et al. (p. 1502; see the Perspective by Ibáñez Insa) show that other compounds—including Na3Cl, Na2Cl, Na3Cl2, NaCl3, and NaCl7 are as stable as NaCl across a range of pressures. Several phases in the Na-Cl system are stable at high pressures and temperatures. [Also see Perspective by Ibáñez Insa] Sodium chloride (NaCl), or rocksalt, is well characterized at ambient pressure. As a result of the large electronegativity difference between Na and Cl atoms, it has highly ionic chemical bonding (with 1:1 stoichiometry dictated by charge balance) and B1-type crystal structure. By combining theoretical predictions and diamond anvil cell experiments, we found that new materials with different stoichiometries emerge at high pressures. Compounds such as Na3Cl, Na2Cl, Na3Cl2, NaCl3, and NaCl7 are theoretically stable and have unusual bonding and electronic properties. To test this prediction, we synthesized cubic and orthorhombic NaCl3 and two-dimensional metallic tetragonal Na3Cl. These experiments establish that compounds violating chemical intuition can be thermodynamically stable even in simple systems at nonambient conditions.