Periodic Trends within Actinyl(VI) Nitrates and Their Structures, Vibrational Spectra, and Electronic Properties

Abstract

A series of actinyl(VI) nitrate salts of the form MAnO₂(NO₃)₃, where M = NH₄⁺ K⁺, Rb⁺, Cs⁺, and Me₄N⁺ and AnO₂²⁺ = U, Np, Pu, and AnO₂(NO₃)₂(H₂O)₂·H₂O, and the uranyl tetranitrates M₂UO₂(NO₃)₄ have been synthesized from aqueous solution and their structures determined using single-crystal X-ray diffraction. Together, these complexes represent an isostructural series of actinide complexes among the salts crystallized with the same charge-compensating cation and have been studied using vibrational spectroscopy including Raman and Fourier-transform infrared. Periodic trends in both the structural properties of these complexes and their vibrational spectra are presented and discussed, in particular the invariant nature of the O≡An≡O asymmetric stretching frequencies observed across the actinyl series. Electronic structure calculations were performed at a variety of levels of theory to aid in the interpretation of the vibrational data and to correlate trends in the data with the underlying electronic properties of these molecules.