High-pressure structures of lithium, potassium, and rubidium predicted by an ab initio evolutionary algorithm

摘要

We have extensively explored the high-pressure structures of lithium (Li), potassium (K), and rubidium (Rb) using an ab initio evolutionary algorithm. For Li, an unexpected cubic P4_1 32 structure containing sixfold coordinated lithium atoms and Li_3 equilateral triangles was discovered to be stable above 300 GPa. This structure is reported for the first time in the elements and shows charge accumulation in the voids of the structure, rather than within the Li_3 triangles. At pressures above the stability field of complex incommensurate phases, the heavier elements K and Rb were predicted to adopt the sequence of I4_1/amd→Cmca → double-hexagonal-close-packed. This sequence parallels the experimentally known structural sequence in Cs, which can be explained by the predominant d character of the valence electrons in K, Rb, and Cs at high-pressures. The major p character at the Fermi level in Li makes it distinct from K, Rb, and Cs.