Anticorrelated Contributions to Pre-edge Features of Aluminate Near-Edge X-ray Absorption Spectroscopy in Concentrated Electrolytes

Ion pairing within complex solutions and electrolytes is a difficult phenomenon to measure and investigate, yet it has significant impact upon macroscopic processes, such as crystal formation. Traditional methods of detecting and characterizing ion pairing are sensitive to contact ion pairs, may require minimum concentrations that limit applicability, and can have difficulty in characterizing solutions with many components. Because of its element specificity and sensitivity to local environment, X-ray absorption near edge structure (XANES) is a promising tool for investigating ion pairing in complex solutions. In concentrated sodium aluminate solutions, a shift in the pre-edge shoulder correlated to sodium concentration is observed, and the physical origins of that shift are investigated using energy specific time-dependent density functional theory of subensembles obtained from ab initio molecular dynamics. Two transitions are found to contribute to the pre-edge feature, yet they are anticorrelated with ...