Ba with Unusual Oxidation States in Ba Chalcogenides under Pressure

The preparation of compounds with novel atomic oxidation states and emergent properties is of fundamental interest in chemistry. As s-block elements, alkali-earth metals invariably show a +2 formal oxidation state at normal conditions, and among them, barium (Ba) presents the strongest chemical reactivity. Herein, we propose that novel valence states of Ba can be achieved in pressure-induced chalcogenides, where it also shows a feature of 5d-elements. First-principles swarm-intelligence structural search calculations identify three novel stoichiometric compounds: BaCh₄ (Ch = O, S) containing Ba²⁺, Ba₃Ch₂ (Ch = S, Se, Te) with Ba⁺ and Ba²⁺, and Ba₂Ch (Ch = Se, Te) with Ba⁺ cations. The pressure-induced drop of the Ba 5d level relative to Ba 6s is responsible for this unusual oxidation state. These compounds display captivating structural characters, such as Ba-centered polyhedra and chain-shaped Ch units. More interestingly still, the interaction between two Ba⁺ ions ensures their structural stability.