Breakdown of the Born-Oppenheimer approximation in solid hydrogen and hydrogen-rich solids

Abstract

Hydrogen has been the subject of intense research following the discovery of high-temperature superconductivity in hydrides, and as a result of continuous efforts to produce solid hydrogen. The Born-Oppenheimer approximation is the central piece of the quantum mechanical description of molecules and solids and it is expected to have its weakest validity in hydrogen containing matter as it is the lightest element of all. The Born-Oppenheimer approximation is almost always assumed in the description of solids. Some beyond Born-Oppenheimer effects are likely included in the state-of-art method used to describe hydrogen-rich materials, but the effects on the electronic structure in solids have not been considered before. Here we compute the beyond Born-Oppenheimer corrections to electron density and report a breakdown of the Born-Oppenheimer approximation in experimentally known hydride superconductor YH6 and in Cs-IV structure of solid hydrogen. In both of these materials, we find a significant transfer of electron density from the volumes surrounding the expected positions of the hydrogen nuclei to volumes in between the nuclei. We expect these results to be the starting point of the beyond Born-Oppenheimer studies of electronic structure in solids, which is likely necessary to understand these forms of hydrogen-containing materials, also having significant technological importance.