Potassium-activated anionic copper and covalent Cu-Cu bonding in compressed K-Cu compounds

Elemental copper and potassium are immiscible under ambient conditions. It is known that pressure is a useful tool to promote the reaction between two different elements by modifying their electronic structure significantly. Here, we predict the formation of four K-Cu compounds (K₃Cu₂, K₂Cu, K₅Cu₂, and K₃Cu) under moderate pressure through unbiased structure search and first-principles calculations. Among all predicted structures, the simulated x-ray diffraction pattern of K₃Cu₂ perfectly matches a K-Cu compound synthesized in 2004. Further simulations indicate that the K-Cu compounds exhibit diverse structural features with novel forms of Cu aggregations, including Cu dimers, linear and zigzag Cu chains, and Cu-centered polyhedrons. Analysis of the electronic structure reveals that Cu atoms behave as anions to accept electrons from K atoms through fully filling 4s orbitals and partially extending 4p orbitals. Covalent Cu-Cu interaction is found in these compounds, which is associated with the sp hybridizations. These results provide insights into the understanding of the phase diversity of alkali/alkaline earth and metal systems.