Prediction of Stable Ground-State Binary Sodium-Potassium Interalkalis under High Pressures

TL;DR

This study uses computational methods to predict stable binary sodium-potassium compounds under high pressure, resolving previous experimental and theoretical discrepancies and discovering new stable phases with unique electronic properties.

Contribution

It provides a comprehensive stability analysis of NaxK compounds under high pressure, identifying new stable phases and clarifying the behavior of NaK and Na2K.

Findings

Na2K is unstable at 5-35 GPa, aligning with experiments.

NaK undergoes pressure-induced decomposition and recombination.

Discovery of new compounds NaK3 and Na3K2 with distinct electronic properties.

Abstract

The complex structures and electronic properties of alkali metals and their alloys provide a natural laboratory for studying the interelectronic interactions of metals under compression. A recent theoretical study (J. Phys. Chem. Lett. 2019, 10, 3006) predicted an interesting pressure-induced decomposition-recombination behavior of the Na2K compound over a pressure range of 10 - 500 GPa. However, a subsequent experiment (Phys. Rev. B 2020, 101, 224108) reported the formation of NaK rather than Na2K at pressures above 5.9 GPa. To address this discordance, we study the chemical stability of different stoichiometries of NaxK (x = 1/4, 1/3, 1/2, 2/3, 3/4, 4/3, 3/2 and 1 - 4) by effective structure searching method combined with first-principles calculations. Na2K is calculated to be unstable at 5 - 35 GPa due to the decomposition reaction Na2K-> NaK + Na, coinciding well with the experiment. NaK undergoes a combination-decomposition-recombination process accompanied by an opposite charge-transfer behavior between Na and K with pressure. Besides NaK, two hitherto unknown compounds NaK3 and Na3K2 are uncovered. NaK3 is a typical metallic alloy, while Na3K2 is an electride with strong interstitial electron localization.