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.