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Yes—at least in computer predictions. A study by Gabriele Saleh and Artem R. Oganov predicted sodium-rich chlorides with unusual compositions, including chlorine assigned a −2 oxidation state. The work concerns materials modeled under extreme compression, not ordinary table salt, and its predicted phases should not be mistaken for compounds experimentally synthesized in that study.
What did the study predict?
Saleh and Oganov used evolutionary crystal-structure prediction calculations to examine alkali subhalides: compounds in which an alkali metal is present in greater proportion than the halogen. Their paper reports an updated phase diagram for sodium-rich chlorides, including Na4Cl3 and two previously undiscovered phases of Na3Cl. The calculations also predicted chlorine atoms with a −2 oxidation state in sodium subchlorides.
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Chemistry World described the modeled pressure range as reaching up to 350 GPa. That figure is the range reported for the calculations, not a universal threshold at which these compounds must form or a measured condition for every prediction. The paper itself characterizes the work more generally as involving pressures of hundreds of gigapascals.
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Why is chlorine at −2 unusual?
In familiar chemistry, chlorine commonly has an oxidation state of −1 in ionic compounds, as it does in sodium chloride. Oxidation states are a way to account for electrons in a compound; they are not a direct measurement of an atom’s literal charge. A predicted −2 state is therefore striking because it departs from the pattern readers learn from ordinary salts.
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Extreme compression can change which arrangements of atoms are energetically stable. Under those conditions, familiar expectations about composition, bonding and oxidation states may not reliably predict the structures that can exist. The headline’s “rewriting the textbooks” language captures the surprise, but the result is better understood as a challenge to simple rules under unusual conditions—not as proof that ordinary chemistry no longer applies.
What was the paper’s broader contribution?
The authors proposed a model to explain the stability of alkali subhalides at high pressure, considering how metallic and ionic bonding interact in these materials. They also tested the model’s predictive ability computationally on A3Y compounds, where A was lithium, sodium or potassium and Y was fluorine, chlorine or bromine.
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Gabriele Saleh told Chemistry World, “High pressure chemistry is unpredictable,” adding, “Most chemical rules break down at high pressure.” Those remarks refer to chemistry under extreme compression, where conventional intuition may fail. They do not mean chemical behavior becomes rule-free; the study’s model is an effort to explain and predict it.
Were the predicted compounds made in a laboratory?
The cited paper reports computational predictions, not experimental synthesis of the specific phases it predicts. Its results identify structures and oxidation-state assignments that calculations suggest could be stable under high pressure. Experimental confirmation is a separate question, and the study should not be cited as proof that these particular phases were synthesized.
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Where the work appeared
The paper, “Alkali subhalides: high-pressure stability and interplay between metallic and ionic bonds,” by Gabriele Saleh and Artem R. Oganov, was first published on 2 December 2015 and appears in Physical Chemistry Chemical Physics, volume 18 (2016), pages 2840–2849. The Royal Society of Chemistry record provides the publication details. Chemistry World covered the predictions on 23 February 2016, and UCL’s related item, dated 6 April 2016, quoted Professor Paul McMillan describing the work as going “beyond the principles of valency established for over 200 years.”
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