Electronic and structural transitions in dense liquid sodium

It has recently been shown that, when high pressures are applied, crystals of lithium and sodium undergo a sequence of phase transitions — including (for sodium) a striking and as yet unexplained pressure-induced drop in the melting temperature. Jean-Yves Raty et al. have now identified the cause of this unusual melting behaviour: it emerges because liquid sodium undergoes a series of transitions similar to those seen in the solid state, but at much lower pressures. Intriguingly, one of these transitions is driven by the opening of a 'pseudogap' in the electronic density of states, the first time such an effect has been seen in a liquid metal. When high pressures are applied, crystals of lithium and sodium undergo a sequence of phase transitions, including a striking pressure-induced drop in the melting temperature. The cause of the unusual melting behaviour has now been identified: it emerges because liquid sodium undergoes a series of transitions similar to those seen in the solid state, but at much lower pressures. One of these transitions is driven by the opening of a 'pseudogap' in the electronic density of states. At ambient conditions, the light alkali metals are free-electron-like crystals with a highly symmetric structure. However, they were found recently to exhibit unexpected complexity under pressure1,2,3,4,5,6. It was predicted from theory1,2—and later confirmed by experiment3,4,5—that lithium and sodium undergo a sequence of symmetry-breaking transitions, driven by a Peierls mechanism, at high pressures. Measurements of the sodium melting curve6 have subsequently revealed an unprecedented (and still unexplained) pressure-induced drop in melting temperature from 1,000 K at 30 GPa down to room temperature at 120 GPa. Here we report results from ab initio calculations that explain the unusual melting behaviour in dense sodium. We show that molten sodium undergoes a series of pressure-induced structural and electronic transitions, analogous to those observed in solid sodium but commencing at much lower pressure in the presence of liquid disorder. As pressure is increased, liquid sodium initially evolves by assuming a more compact local structure. However, a transition to a lower-coordinated liquid takes place at a pressure of around 65 GPa, accompanied by a threefold drop in electrical conductivity. This transition is driven by the opening of a pseudogap, at the Fermi level, in the electronic density of states—an effect that has not hitherto been observed in a liquid metal. The lower-coordinated liquid emerges at high temperatures and above the stability region of a close-packed free-electron-like metal. We predict that similar exotic behaviour is possible in other materials as well.