Spectroscopic Properties of Americium(III) in Mineral Acid Media.

Abstract

We report the preparation and optical characterization of three solutions of Am(III) in common aqueous (aq.) mineral acids (HCl, HNO3, and HBr), including absorption, emission, and Raman vibrational analyses. To our knowledge, this study provides the first detailed absorption spectra of Am(III) spanning the entire UV/vis/NIR region in these mineral acids reported since the 1960s. Using this high-resolution absorption data, provided in an open access format for the broader field, we build on prior work by Carnall and others to provide detailed optical analysis including all transition assignments. This work also includes the first reported absorption spectrum of Am(III) in aq. HBr. Characteristic Am(III) luminescence could be detected from all three samples. These are the first reports of emission from Am(III) in these acid systems, which build on prior emission reports collected from aq. HClO4 solutions. The acquired emission spectra display anion-dependent shifting of the visible-region transitions by up to 21 nm from their predicted positions, akin to the nephelauxetic effect. The shift magnitude trends linearly according to acid pKa and more generally according to the transition metal spectrochemical series. These ligand field effects, coupled with luminescence lifetime experiments, indicate that weak Am-X interactions persist in solution.