Origin of the anomalous semiconducting behaviour in dense lithium (1802.08985v3)

Abstract: Experimentally, it is known that lithium undergoes a metal to semiconductor transition at about 80 GPA and a reentrant semiconductor to metal transition near 120 GPA. This unusual behaviour has been attributed to the formation of high-pressure electrides in the Li-\textit{Aba}2 phase. Using the accurate wave function based quantum Monte Carlo (DMC) method, we show that the valence charge distribution of the Li-\textit{Aba}2 phase is incompatible with an insulating or semiconducting ground state. At DMC level, the most stable phase at 100 GPA is an orthorhombic oP24 structure with Pbca symmetry whose valence charge density shows an electride paired distribution, in correspondence with the theoretical predictions of Neaton and Ashcroft [Nature 00, 141 (1999)]. Here, we propose the electride pairing in the oP24-(Pbca) phase as the origin of the semiconducting behaviour observed in diamond anvil cell experiments.