Unexpected giant negative area compressibility in palladium diselenide

Negative area compressibility (NAC) is a counterintuitive ‘squeeze–expand’ behavior in solids that is very rare but attractive due to possible pressure–response applications and coupling with rich physicochemical properties. Herein, NAC behavior is reported in palladium diselenide with a large magnitude and wide pressure range. We discover that, apart from the rigid flattening of layers that has been generally recognized, the unexpected giant NAC effect in PdSe(2) largely comes from anomalous elongation of intralayer chemical bonds. Both structural variations are driven by intralayer-to-interlayer charge transfer with enhanced interlayer interactions under pressure. Our work updates the mechanical understanding of this anomaly and establishes a new guideline to explore novel compression-induced properties.