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Using a variable-composition  ab initio  evolutionary algorithm implemented in the USPEX code, we have performed a systematic search for stable compounds in the Ca-Bi system at different pressures. In addition to the well-known  tI 12-Ca 2 Bi and  oS 12-CaBi 2 , a few more structures were found by our calculations, among which phase transitions were also predicted in Ca 2 Bi ( tI 12 →  oI 12 →  hP 6), Ca 3 Bi 2  ( hP 5 →  mC 20 →  aP 5) and CaBi ( tI 2 →  tI 8), as well as a new phase (Ca 3 Bi) with a  cF 4 structure. All the newly predicted structures can be both dynamically and thermodynamically stable with increasing pressure. The superconductive properties of  cF 4-CaBi 3 ,  tI 2-CaBi and  cF 4-Ca 3 Bi were studied and the superconducting critical temperature  T c   can be as high as 5.16, 2.27 and 5.25 K, respectively. Different superconductivity behaviors with pressure increasing have been observed by further investigations.

Rich stoichiometries of stable Ca-Bi system: Structure prediction and superconductivity