Quantum chemical study of reaction mechanism between plutonium and nitrogen

The study of the reaction between plutonium and nitrogen is helpful in further understanding the interaction between plutonium and air molecules. Currently, there is no research on the microscopic reaction mechanism of plutonium nitridation reactions. Therefore, the microscopic mechanism of the Pu with N₂ gas phase reaction is explored in this study, based on density functional theory (DFT) using different basis functions. In this paper, the geometry of stationary points on the potential energy surface is optimized. In addition, the transition states are verified by frequency analysis and intrinsic reaction coordination (IRC). Finally, we obtained the reaction potential energy curve and micro reaction pathways. Analysis of the reaction mechanism shows that the reaction of Pu with N₂ has two pathways. Pathway 1 (Pu + N₂ → R1 → TS1 → PuN₂) has a T-shaped transition state and pathway 2 (Pu + N₂ → R2 → TS2 → PuN + N) has an L-shaped transition state. Both transition states have only one imaginary frequency. According to the comparison of the energy at each stagnation point along the two pathways, and the heat energy emitted by the two reaction paths, we found that pathway 1 is the main reaction pathway. The nature of Pu-N bonding evolution along the pathways was studied by atoms in molecules (AIM) and electron localization function (ELF) topological approaches. In order to analyze the role of the plutonium atom 5f orbital in the reaction, the variation in density state along the pathways was measured. Results show that the 5f orbital mainly contributes to the formation of Pu-N bonds, and the influence of temperature on the reaction rate is revealed by calculating the rate constants of the two reaction pathways.