Decomposition and Recombination of Binary Interalkali Na₂K at High Pressures

Under compression, "'simple'" alkali metals and their alloys exhibit complex structural and electronic properties, leading to fundamental interest in their high-pressure behaviors. Here, the swarm-intelligence structure-searching method was employed to identify the high-pressure phases of binary interalkali Na₂K, which has long been known to possess a MgZn₂-Laves phase at ambient pressure, but the high-pressure behavior remains elusive. We uncovered four new structures over a pressure range of 10-500 GPa, although the compound was found to become unstable upon decomposition into Na and K from 37 to 273 GPa. In phases before decomposition, the electrons were gradually delocalized with an increase in pressure and there was charge transfer from K to Na, whereas in phases after recombination, the electrons were gradually localized into the interstitials of the crystals, showing the unexpected opposite trend of charge transfer from Na to K, remarkably, where K was found to exhibit an oxidation state beyond the -1 valence state. The results can improve our understanding of the interaction and evolution of s electrons under compression.