Competition between superconductivity and molecularization in quantum nuclear behavior of Lanthanum Hydride

Abstract: Lanthanum hydride is the superconductor with the highest known critical temperature. It is believed that the superconductivity is of standard BCS-type, with electrons forming Cooper pairs and opening the superconducting band gap. Here we show that the BCS electron pairing is in competition with an alternative pairing: covalent bonding. We show that the covalent pairing is favored at lower pressures, the superconducting cubic phase becomes unstable as pressure is reduced. Previous calculations based on static relaxation neglect three factors, all of which are important in stabilizing the cubic phase. Finite temperature plays a role, and two quantum effects are also important - the nuclear wavefunction contributes to destablizing the H$_2$ molecules, and the zero-point pressure means that calculated pressures are significantly overestimated by standard methods. We demonstrate these phenomena using Born-Oppenheimer and path-integral molecular dynamics: these give the same qualitative picture, with nuclear quantum effects (NQE) increasing the transition pressure significantly. This competition between molecularization and superconducting gap formation is the fundamental reason why hydride superconductors have so far been found only at high pressure.