Chemical Shift of the Kα1 and Kα2 Lines of the X-ray Emission Spectrum of Yb(II)/Yb(III) Fluorides: a Quantum-Chemical Investigation

Abstract

Chemical shifts of the K_α1 and K_α2 lines (the 2p_3/2 → 1s_1/2 and 2p_1/2 → 1s_1/2 transitions, respectively) of the X-ray emission spectrum of the Yb atom in fluorides have been calculated by ab initio modeling the electronic structure. The valence transition Yb(II) → Yb(III) has been analyzed by examples of YbF₂, YbF₃, and Yb₂F₄ molecules and YbF₂⁺ cation. The relativistic pseudopotential and basis sets corresponding to it have been constructed for the ytterbium atom. They were used in calculations by the two-component noncollinear version of the density functional theory (DFT) with the PBE0 exchange-correlation functional. Results for the three-coordinated Yb(II) in the FYbF₂YbF dimer demonstrated a very weak dependence of the chemical shift on the coordination number of the Yb atom and on the molecular association of ytterbium difluoride. Chemical shifts of the X-ray emission spectrum for the ytterbium compound are related mainly to the change in the occupation of the 4 f shell.