Puzzling Lack of Temperature Dependence of the PuO2 Magnetic Susceptibility Explained According to Ab Initio Wave Function Calculations

摘要

The electronic structure and the magnetic properties of solid PuO2 are investigated by wave function theory calculations, using a relativistic complete active space (CAS) approach including spin-orbit coupling. The experimental magnetic susceptibility is well reproduced by calculations for an embedded PuO812- cluster model. The calculations indicate that the surprising lack of temperature dependence of the magnetic susceptibility chi of solid PuO2 can be rationalized based on the properties of a single Pu4+ ion in the cubic ligand field of the surrounding oxygen ions. Below similar to 300 K, the only populated state is the nonmagnetic ground state, leading to standard temperature-independent paramagnetism (TIP). Above 300 K, there is an almost perfect cancellation of temperature-dependent contributions to chi that depends delicately on the mixing of ion levels in the electronic states, their relative energies, and the magnetic coupling between them.