Pu3M和PuM3 (M=Ga,In, Sn,Ge)化合物的电子结构和形成热

采用全势线性缀加平面波(FPLAPW)方法, 在广义梯度近似(GGA)+自旋轨道耦合(SOC)+自旋极化(SP)下计算了具有AuCu3构型的Pu3M和PuM3 (M=Ga, In, Sn, Ge)化合物的平衡结构、电子结构和形成热. 计算的晶格常数与实验值符合得很好; 态密度分析表明Pu 和M 原子轨道间的杂化作用决定于Pu 6d-Pu 5f、Mp-Pu 6d和Msp-M sp轨道杂化之间的竞争, 而这种竞争又依赖于M的含量; 电负性差和电子杂化效应是影响Pu3M和PuM3化合物形成热和稳定性的两个重要因素, 电负性差越大, M的s、p带中心距费米能级越远, Pu3M(PuM3)化合物的形成热越负, 稳定性越高.

Electronic Structure and Formation Heat of Pu3M and PuM3(M=Ga,In,Sn and Ge)Compounds

The equilibrium structure, electronic structure, and formation heat of Pu3M (PuM3) (M=Ga, In, Sn and Ge) compounds with AuCu3 structure have been calculated using full potential linear augmented plane wave (FPLAPW) method with generalized-gradient approximation (GGA) including spin-orbit coupling (SOC) and spin polarized (SP). The calculated lattice parameters are in good agreement with experimental values.Density of state analysis shows hybridization effects between Pu andMare governed by the competitions depending on the M amount: Pu 6d-Pu 5f, M p-Pu 6d, and M sp-M sp interactions. Electronegativity difference and electronic hybridization effect are two important factors to influence the formation heat and stability of Pu3M(PuM3) compounds. The larger the electronegativity difference and the lower the M s-band or p-band center relative to the Fermi heat, the more negative is the formation energy and the more stable are Pu3M(PuM3) compounds.