The quantum mechanical treatment of both electrons and nuclei is crucial in nonadiabatic dynamical processes such as proton-coupled electron transfer. The nuclear−electronic orbital (NEO) method provides an elegant framework for including nuclear quantum effects beyond the Born–Oppenheimer...
Predicting accurate nuclear magnetic resonance chemical shieldings relies upon cancellation of different types of errors between the theoretically calculated shielding constant of the analyte of interest and the reference. Often, the intrinsic error in computed shieldings due to basis sets...
Understanding mechanistic pathways to radiolytic hydrogen generation by metal oxyhydroxide nanomaterials is challenging because of the difficulties of distinguishing key locations of OH bond scission, from structural interiors to hydroxylated surfaces to physi-sorbed water molecules. Here we...
Tetrahedrally coordinated aluminate Al(OH)4- and dialuminate Al2O(OH)62- anions are considered to be major species in aluminum-rich alkaline solutions. However, their relative abundance remains difficult to spectroscopically quantify due local structure similarities and poorly understood effects...
The stability of aluminum oxyhydroxide (AlOOH, boehmite) to radiolysis and dehydration to alumina (γ-Al2O3) under vacuum was investigated using TGA followed by detailed, structural analysis with Raman, powder X-Ray Diffraction (pXRD), high energy X-Ray Diffraction (heXRD), 27Al Magic Angle Spinning...
The incorporation of relatively minor impurity metals onto metal (oxy)hydroxides can strongly impact solubility. In complex highly alkaline multicomponent radioactive tank wastes such as those at the Hanford Nuclear Reservation, tests indicate that the surface area-normalized dissolution rate of...
In highly alkaline “water-in-salt” Na2O/Al2O3/H2O solutions where the monomeric Al(OH)4– anion dominates, isolation of transitional species that seed crystallization of sodium aluminate salt hydrates has been challenging. For example, discrimination of dimeric [for example, Al2O(OH)62–] species via...
Electrolyte solutions in alkaline nuclear waste contain aluminate, hydroxide, nitrate and nitrite with sodium as the predominant counterion. The salts of these ions are highly soluble, so the liquids are highly concentrated. This study found that there is a substantial incompatibility between the...
The recently developed real-time nuclear–electronic orbital (RT-NEO) approach provides an elegant framework for treating electrons and selected nuclei, typically protons, quantum mechanically in nonequilibrium dynamical processes. However, the RT-NEO approach neglects the motion of the other nuclei...
The molecular speciation of aluminum (Al3+) in alkaline solutions is fundamental to its precipitation chemistry within a number of industrial applications that include ore refinement and industrial processing of Al wastes. Under these conditions, Al3+ is predominantly Al(OH)4–, while at high [Al3+]...
X-ray, energetic photon, and electron irradiation can ionize and electronically excite target atoms and molecules. These excitations undergo complicated relaxation and energy-transfer processes that ultimately determine the manifold system responses to the deposited excess energy. In weakly bound...
The radiolysis of liquid water and the radiation-matter interactions that happen in aqueous environments are important to the elds of chemistry, materials, and environmental sciences, as well as biological and physiological response to extreme conditions and medical treatments. The initial stage of...
The role of oligomeric aluminate species in the precipitation of aluminum (Al) phases such as gibbsite (α-Al(OH)3) from aqueous hydroxide solutions remains unclear and difficult to probe directly, despite its importance for developing accurate predictions of Al solubility in highly alkaline systems...
Understanding, controlling, and preventing aggregation of suspended particles is of fundamental importance in a number of scientific and industrial fields. There are several methods for analyzing aggregate morphology and aggregation kinetics, but small-angle scattering (SAS) techniques provide...
The iron oxy-hydroxide lepidocrocite (𝛾γ-FeOOH) is an abundant mineral critical to a number of chemical and technological applications. Of particular interest are the ground state and finite temperature magnetic order and the subsequent impact this has upon crystal properties. The magnetic...