Mixing unmixables: Unexpected formation of Li-Cs alloys at low pressure

Contrary to the empirical Miedema and Hume-Rothery rules and a recent theoretical prediction, we report experimental evidence on the formation of Li-Cs alloys at very low pressure (>0.1 GPa). We also succeeded in synthesizing a pure nonstoichiometric and ordered crystalline phase from an approximately equimolar mixture and resolved its structure using the maximum entropy method. The new alloy has a primitive cubic cell with the Li atom situated in the center and the Cs at the corners. This structure is stable to at least 10 GPa and has an anomalously high coefficient of thermal expansion at low pressure. Analysis of the valence charge density shows that electrons are donated from Cs to the Li “p”-orbitals, resulting in a rare formal oxidation state of −1 for Li. The observation indicates the diversity in the bonding of the seeming simple group I Li element.