Symmetry and stability of plutonium: the influence of electronic structure.
Using first-principles density-functional theory, we calculate the bond strengths between the 12 nearest neighbors in delta plutonium for both pure Pu and a Pu-3.7 at. % Ga alloy. Our results for pure Pu reveal a structure with the monoclinic space group Cm rather than face-centered cubic Fm3m, showing that the anomalously large anisotropy of delta plutonium is a consequence of greatly varying bond strengths between the 12 nearest neighbors. Further results for a Pu-3.7 at. % Ga alloy show that the nearest-neighbor bond strengths around a Ga atom are more uniform. Hence, our calculations address (i) why the ground state of Pu is monoclinic, (ii) why distortions of the delta phase are viable, with considerable implications for the behavior of the material as it ages due to anisotropic response to self-irradiation, and (iii) why Ga stabilizes face-centered cubic delta-Pu.