Phase Stability in heavy f-Electron Metals from First-Principles Theory

Abstract

AbstractThe structural phase stability of heavy f-electron metals is studied by means of density-functional theory (DFT). These include temperature-induced transitions in plutonium metal as well as pressure-induced transitions in the trans-plutonium metals Am, Cm, Bk, and Cf. The early actinides (Th-Np) display phases that could be rather well understood from the competition of a crystal-symmetry breaking mechanism (Peierls distortion) of the 5f states and electrostatic forces, while for the trans-plutonium metals (Am-Cf) the ground-state structures are governed by 6d bonding. We show in this paper that new physics is needed to understand the phases of the actinides in the volume range of about 15-30 Å3. At these volumes one would expect, from theoretical arguments made in the past, to encounter highly complex crystal phases due to a Peierls distortion. Here we argue that the symmetry reduction associated with spin polarization can make higher symmetry phases competitive. Taking this into account, DFT is shown to describe the well-known phase diagram of plutonium and also the recently discovered complex and intriguing high-pressure phase diagrams of Am and Cm. The theory is further applied to investigate the behaviors of Bk and Cf under compression.