Until very recently, helium had remained the last naturally occurring element that was known not to form stable solid compounds. Here we propose and demonstrate that there is a general driving force for helium to react with ionic compounds that contain an unequal number of cations and anions. The corresponding reaction products are stabilized not by local chemical bonds but by long-range Coulomb interactions that are significantly modified by the insertion of helium atoms, especially under high pressure. This mechanism also explains the recently discovered reactivity of He and Na under pressure. Our work reveals that helium has the propensity to react with a broad range of ionic compounds at pressures as low as 30 GPa. Since most of the Earth’s minerals contain unequal numbers of positively and negatively charged atoms, our work suggests that large quantities of He might be stored in the Earth’s lower mantle.

Xenon difluoride is the first and the most stable of hundreds of noble-gas (Ng) compounds. These compounds reveal the rich chemistry of Ng's. No stable compound that contains a Ng-Ng bond has been reported previously. Recent experiments have shown intriguing behaviors of this exemplar compound under high pressure, including increased coordination numbers and an insulator-to-metal transition. None of the behaviors can be explained by electronic-structure calculations with fixed stoichiometry. We therefore conducted a structure search of xenon-fluorine compounds with various stoichiometries and studied their stabilities under pressure using first-principles calculations. Our results revealed, unexpectedly, that pressure stabilizes xenon-fluorine compounds selectively, including xenon tetrafluoride, xenon hexafluoride, and the xenon-rich compound XeF. Xenon difluoride becomes unstable above 81 GPa and yields metallic products. These compounds contain xenon-xenon covalent bonds and may form intercalated graphitic xenon lattices, which stabilize xenon-rich compounds and promote the decomposition of xenon difluoride.

Main group elements usually assume a typical oxidation state while forming compounds with other species. Group I elements are usually in the þ 1 state in inorganic materials. Our recent work reveals that pressure may make the inner shell 5p electrons of Cs reactive, causing Cs to expand beyond the þ 1 oxidation state. Here we predict that pressure can cause large electron transfer from light alkali metals such as Li to Cs, causing Cs to become anionic with a formal charge much beyond À 1. Although Li and Cs only form alloys at ambient conditions, we demonstrate that these metals form stable intermetallic Li n Cs (n ¼ 1-5) compounds under pressures higher than 100 GPa. Once formed, these compounds exhibit interesting structural features, including capped cuboids and dimerized icosahedra. Finally, we explore the possibility of superconductivity in metastable LiCs and discuss the effect of the unusual anionic state of Cs on the transition temperature.

Additional electrons can drastically change the bonding trend of light elements. For example, N atoms in alkali metal azides form the linear N3(-) anions instead of N2 molecules with the introduction of additional electrons. The effect of the additional electrons on the polymerization of N under pressure is important and thus far unclear. Using first principles density functional methods and the particle swarm optimization structure search algorithm, we systematically study the evolution of LiN3 structures under pressures up to 600 GPa. A stable structure featuring polymerized N under pressures higher than 375 GPa is identified for the first time. It consists of zig-zag N polymer chains that are formed by N5(-) five-member rings sharing N-N pairs. Throughout the stable pressure range, the structure is insulating and consists of N atoms in sp(3) hybridizations. Comparing with the atomic and electronic structures of previous phases, our study completes the structural evolution of LiN3 under pressure and reveals the structural changes which are accompanied and driven by the change of atomic orbital hybridization, first from sp to sp(2) and then from sp(2) to sp(3).