Anharmonicity and the isotope effect in superconducting lithium at high pressures: A first-principles approach

Recent experiments [A. M. Schaeffer, Proc. Natl. Acad. Sci. USA 112, 60 (2015)10.1073/pnas.1412638112] have shown that lithium presents an extremely anomalous isotope effect in the 15-25 GPa pressure range. In this article we have calculated the anharmonic phonon dispersion of Li7 and Li6 under pressure, their superconducting transition temperatures, and the associated isotope effect. We have found a huge anharmonic renormalization of a transverse acoustic soft mode along ΓK in the fcc phase, the expected structure at the pressure range of interest. In fact, the anharmonic correction dynamically stabilizes the fcc phase above 25 GPa. However, we have not found any anomalous scaling of the superconducting temperature with the isotopic mass. Additionally, we have also analyzed whether the two lithium isotopes adopting different structures could explain the observed anomalous behavior. According to our enthalpy calculations including zero-point motion and anharmonicity it would not be possible in a stable regime.