Structure of Aqueous Scandium(III) Nitrate Solution by Large-Angle X-ray Scattering Combined with Empirical Potential Refinement Modeling, X-ray Absorption Fine Structure, and Discrete Variational Xα Calculations

Abstract

Abstract Large-Angle X-ray scattering (LAXS) and Sc K X-ray absorption near-edge structure (XANES) measurements are made at room temperature on a 1 M (= mol dm−3) Sc(NO3)3 aqueous solution. The X-ray interference function is subjected to an empirical potential structure refinement (EPSR) modeling to extract the site-site pair correlation functions, the coordination number distribution, and the spatial density functions (three-dimensional structure). The LAXS analysis combined with EPSR reveals that Sc3+ is surrounded by six or seven water molecules and one oxygen atom of NO3− with an Sc3+-Ow (H2O) and Sc3+-ON (NO3−) distance of 2.14 Å. NO3− has a weak solvation shell with a broad distribution of coordination numbers with the highest population of nine at an N-Ow distance of 3.66 Å. Solvent water forms the tetrahedral network structure. The XANES spectrum is compared with simulated spectra on various coordination geometries of an ScO7 moiety with a discrete variational Xα (DV-Xα) molecular orbital (MO) method. A distorted monocapped trigonal prism structure of Sc3+ best reproduced the experimental pre-peak due to the Sc 1s → 3d transition in the XANES spectrum.