Electride behavior at high pressure in silicon and other elements in solid and liquid phases

Abstract

Electrides are materials in which some of the electrons are localized at the interstitial sites rather than around the atoms or along atomic bonds. Most elemental electrides are either alkali metals or alkaline-earth metals because of their low ionization potential. In this work, we report that elemental silicon becomes an electride at pressures exceeding 400 GPa. With {\it ab initio} molecular dynamics (MD) simulations, we study this behavior for silicon, sodium, potassium, and magnesium at high pressure and temperature. We performed simulations for liquids and ten crystal structures. Charge density and electron localization functions (ELF) are analyzed for representative configurations extracted from the MD trajectories. By analyzing a variety of electride structures, we suggest the following quantitative thresholds for the ELF and charge density in each interstitial site to classify high-pressure electrides: (1) the maximum ELF value should be greater than 0.7, (2) there should be at least 0.9 electrons near the ELF basin, and (3) the Laplacian charge density, $\nabla^2 \rho(\mathbf{r}_0)$, should be negative with magnitude greater than $10^{-3}\ e/\mathrm{bohr}^5$. Finally, we compute X-ray diffraction patterns to determine the degree to which they are affected by the electride formation. Overall, this framework could become a benchmark for future theoretical and experimental studies on electrides.