Density-functional theory for f-electron systems: the α-γ phase transition in cerium.
The isostructural α-γ phase transition in cerium is analyzed using density-functional theory with different exchange-correlation functionals, in particular the PBE0 hybrid functional and the exact-exchange plus correlation in the random-phase approximation [(EX+cRPA)@PBE0] approach. We show that the Hartree-Fock exchange part of the hybrid functional gives rise to two distinct solutions at zero temperature that can be associated with the α and γ phases of cerium. However, despite the relatively good structural and magnetic properties, PBE0 predicts the γ phase to be the stable phase at ambient pressure and zero temperature, in contradiction with low temperature experiments. EX+cRPA reverses the energetic ordering, which emphasizes the importance of correlation for rare-earth systems.
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin, Germany.
Marco
M
Casadei
Xinguo
X
Ren
Patrick
P
Rinke
Angel
A
Rubio
Matthias
M
Scheffler
D002563:Cerium / Q000737:chemistry*; D008956:Models, Chemical; D044367:Phase Transition; D011789:Quantum Theory; D013816:Thermodynamics
D002563:Cerium