Unexpected Stable Stoichiometries of Sodium Chlorides

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Science  20 Dec 2013:
Vol. 342, Issue 6165, pp. 1502-1505
DOI: 10.1126/science.1244989

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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.


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.

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