Ab initio study of ABiO3 (A = Ba, Sr, Ca) under high pressure

27.09.2018

Using ab initio crystal structure prediction we study the high-pressure phase diagram of ABiO3 bismuthates (A = Ba, Sr, Ca) in a pressure range up to 100 GPa.

 

Using ab initio crystal structure prediction we study the high-pressure phase diagram of ABiO3 bismuthates (A = Ba, Sr, Ca) in a pressure range up to 100 GPa. All compounds show a transition from the low-pressure perovskite structure to highly distorted, low-symmetry phases at high pressures (PD transition), and remain charge-disproportionated and insulating up to the highest pressure studied. The PD transition at high pressures in bismuthates can be understood as a combined effect of steric arguments and of the strong tendency of bismuth to charge-disproportionation. In fact, distorted structures permit to achieve a very efficient atomic packing, and at the same time, to have Bi-O bonds of different lengths. The shift of the PD transition to higher pressures with increasing cation size within the ABiO3 series can be explained in terms of chemical pressure.

 

Phys. Rev. B 98, 115158, DOI: 10.1103/PhysRevB.98.115158

 

 

Total and atom-projected DOS for ABiO3 compounds before and after the PD transition: 22 GPa for CaBiO3, 25GPa for SrBiO3, and 45 GPa for BaBiO3, calculated with the HSE functional;the structures were optimized at the PBE level. Bi atoms are divided into formal Bi3+ and Bi5+ valences. For the sake of clarity the Bi-DOS is multiplied by a factor of 15. (© PhysRevB)