Insights into the Mechanism of Neptunium Oxidation to the Heptavalent State.

Neptunium can exist in multiple oxidation states, including the rare and poorly understood heptavalent form. In this work, we monitored the formation of heptavalent neptunium [Np(VII)O4(OH)2]3- during ozonolysis of aqueous MOH (M=Li, Na, K) solutions using a combined experimental and theoretical approach. All experimental reactions were closely monitored via absorption and vibrational spectroscopy to follow both the oxidation state and the speciation of neptunium guided by the calculated vibrational frequencies for various neptunium species. The mechanism of the reaction partly involves oxidative dissolution of transient Np(VI) oxide/hydroxide solid phases, the identity of which are dependent on the co-precipitating counter-cation Li+/Na+/K+. Additional calculations suggest that the most favorable energetic pathway occurs through the reaction of a [Np(V)O2(OH)4]3- with the hydroxide radical to form [Np(VI)O2(OH)4]2-, followed by an additional oxidation with HO⋅ to create [Np(VII)O4(OH)2]3-.

Synthesis, characterization, and density functional theory investigation of (CH6N3)2[NpO2Cl3] and Rb[NpO2Cl2(H2O)] chain structures.

The actinyl tetrachloro complex [An(V/VI)O2Cl4]2-/3- tends to form discrete molecular units in both solution and solid state materials, but related aquachloro complexes have been observed as both discrete coordination compounds and 1-D chain topologies. Subtle differences in the inner sphere coordination significantly influence the formation of structural topologies in the actinyl chloride system, but the exact reasoning for these variations has not been delineated. In the current study, we present the synthesis, structural characterization, and vibrational analysis of two 1-D neptunyl(V) chain compounds: (CH6N3)2[NpO2Cl3] (Np-Gua) and Rb[NpO2Cl2(H2O)] (Np-Rb). Bonding and non-covalent interactions (NCIs) in the systems were evaluated using periodic Density Functional Theory (DFT) to link these properties to related phases. We observed ∼6.5% and ∼3.9% weakening of NpO bonds in Np-Gua and Np-Rb compared to the reference Cs3[NpO2Cl4]. NCI analysis distinguished specific assembly modes, where Np-Gua was connected via hydrogen bonding (N-H⋯Cleq and N-H⋯Oyl) and Np-Rb contained both cation interactions (Rb+⋯Oyl and Rb+⋯Cleq) and hydrogen bonding (Oeq-H⋯Oyl) networks. Thermodynamically viable formation pathways for both compounds were explored using DFT methodology. The [NpO2Cl4](aq)3- and [NpO2Cl3(H2O)](aq)2- substructures were identified as precursors to Np-Gua and [NpO2Cl3(H2O)](aq)2- and [NpO2Cl2(H2O)2](aq)- were isolated as the primary building units of Np-Rb. Finally, we utilized DFT to analyze the vibrational modes for Np-Gua and Np-Rb, where we found evidence of the NpO bond weakening within the Np(V) chain structures compared to [NpO2Cl4]3-.

Three-Dimensional Noncovalent Interaction Network within [NpO2Cl4]2- Coordination Compounds: Influence on Thermochemical and Vibrational Properties.

Noncovalent interactions (NCIs) can influence the stability and chemical properties of pentavalent and hexavalent actinyl (AnO2+/2+) compounds. In this work, the impact of NCIs (actinyl-hydrogen and actinyl-cation interactions) on the enthalpy of formation (ΔHf) and vibrational features was evaluated using Np(VI) tetrachloro compounds as the model system. We calculated the ΔHf values of these solid-state compounds through density functional theory+ thermodynamics (DFT+ T) and validated the results against experimental ΔHf values obtained through isothermal acid calorimetry. Three structural descriptors were evaluated to develop predictors for ΔHf, finding a strong link between ΔHf and hydrogen bond energy (EHtotal) for neptunyl-hydrogen interactions and total electrostatic attraction energy (Eelectrostatictotal) for neptunyl-cation interactions. Finally, we used Raman spectroscopy together with bond order analysis to probe Np=O bond perturbation due to NCIs. Our results showed a strong correlation between the degree of NCIs by axial oxygen and red-shifting of Np=O symmetrical stretch (ν1) wavenumbers and quantitatively demonstrated that NCIs can weaken the Np=O bond. These properties were then compared to those of related U(VI) and Np(V) phases to evaluate the effects of subtle differences in the NCIs and overall properties. In general, the outcomes of our study demonstrated the role of NCIs in stabilizing actinyl solid materials, which consequently governs their thermochemical behaviors and vibrational signatures.