High‐pressure phases of sno and pbo: A density functional theory combined with an evolutionary algorithm approach

Tin monoxide, SnO, and its analog, lead monoxide, PbO, have the same tetragonal P4/nmm structure, shaped by nonbonding dispersion forces and lone pairs. The high‐pressure phases of SnO and PbO have been explored in several experimental and theoretical studies, with conflicting results. In this study, the high‐pressure structures of SnO and PbO are investigated using density functional theory calculations combined with an evolutionary algorithm to identify novel high‐pressure phases. We propose that the monoclinic P21/m SnO and orthorhombic Pmmn PbO phases, which are metastable at 0 GPa, are a slight rearrangement of the tetragonal P4/nmm‐layered structure. These orthorhombic (and their closely related monoclinic) phases become more favored than the tetragonal phase upon compression. In particular, the transition pressures to the orthorhombic γ‐phase Pmn21 of SnO/PbO and the monoclinic phase P21/m of SnO are found to be consistent with experimental studies. Two new high‐pressure SnO/PbO polymorphs are predicted: the orthorhombic Pbcm phase of SnO and the monoclinic C2/m of PbO. These phases are stabilized in our calculations when P > 65 GPa and P > 50 GPa, respectively. The weakening of the lone pair localization and elastic instability are the main drivers of pressure‐induced phase transitions. Modulations of the SnO/PbO electronic structure due to structural transitions upon compression are also discussed.