Exploring the Limits of Superconductivity in Metal-Stuffed B-C Clathrates via Ionic Lattice Anharmonicity

Abstract: Metal-stuffed B-C compounds with sodalite clathrate structure have captured increasing attention due to their predicted exceptional superconductivity above liquid nitrogen temperature at ambient pressure. However, by neglecting the quantum lattice anharmonicity, the existing studies may result in an incomplete understanding of such a lightweight system. Here, using state-of-the-art ab initio methods incorporating quantum effects and machine learning potentials, we revisit the properties of a series of $XY\text{B}{6}\text{C}{6}$ clathrates where $X$ and $Y$ are metals. Our findings show that ionic quantum and anharmonic effects can harden the $E_g$ and $E_u$ vibrational modes, enabling the dynamical stability of 15 materials previously considered unstable in the harmonic approximation, including materials with previously unreported $(XY)^{1+}$ state, which is demonstrated here to be crucial to reach high critical temperatures. Further calculations based on the isotropic Migdal-Eliashberg equation demonstrate that the $T_c$ values for $\text{KRbB}{6}\text{C}{6}$ and $\text{RbB}{3}\text{C}{3}$ among these stabilized compounds are 87 and 98 K at 0 and 15 GPa, respectively, both being higher than $T_c$ of 77 K of $\text{KPbB}{6}\text{C}{6}$ at the anharmonic level. These record-high $T_c$ values, surpassing liquid nitrogen temperatures, emphasize the importance of anharmonic effects in stabilizing B-C clathrates with large electron-phonon coupling strength and advancing the search for high-$T_c$ superconductivity at (near) ambient pressure.