Exploring the Ring-Opening Pathways in the Reaction of Morpholinyl Radicals with Oxygen Molecule

Quantum chemistry calculations using hybrid density functional theory and the coupled-cluster method have been performed to investigate the ring-opening pathways in the oxidation of morpholine (1-oxa-4-aza-cyclohexane). Hydrogen abstraction can form two different carbon-centered radicals, morpholin-2-yl or morpholin-3-yl, or the nitrogen-centered radical, morpholin-4-yl, none of which are found to have low-energy pathways to ring-opening. Extensive exploration of multiple reaction pathways following molecular oxygen addition to these three radicals revealed two competitive low energy pathways to ring-opening. Addition of O₂ to either carbon-centered radical, followed by a 1,4-H shifting mechanism can yield a long-lived cyclic epoxy intermediate, susceptible to ring-opening, following further radical attack. In particular, the second pathway begins with O₂ attack on morpholin-2-yl, followed by a 1,5-H shift and a unimolecular ring-opening without having to overcome a high barrier, releasing a significant amount of heat in the overall ring-opening reaction. The calculations provide valuable context for the development of mechanisms for the low temperature combustion chemistry of nitrogen and oxygen-containing fuels

Atomic-Scale Structure and Stability of the Low-Index Surfaces of Pyrochlore Oxides

The multifunctional properties of complex ternary oxides such as pyrochlores are often influenced by surface structure. Optimizing the surface-driven attributes of these materials necessitates a detailed understanding of the structure and chemical composition of those surfaces. Here we report atomistic simulations elucidating the diverse atomic-scale structures of a set of low-index surfaces [(100), (110), (111), and (112)] in pyrochlore compounds as a function of both A and B cation chemistry. In pyrochlores, the low-index facets are all dipolar, requiring the introduction of surface defects to eliminate the surface dipole. We find that, due to the corresponding higher coordination of the surface cations, the (110) facet is the most energetically stable in all of the compounds considered, an interesting contrast to fluorite, in which the (111) surface is most stable. We also reveal a correlation between the surface energy and the energy to disorder the pyrochlore as a function of B cation chemistry, implying a similar physical origin for the two phenomena. Further, we find that surface rumpling is common across all pyrochlore compounds. An even more interesting feature emerging at these surfaces is the formation of extended structural defects such as steps and trenches, which are found to be stable after high-temperature annealing. As the formation of these features is a consequence of surface defects introduced to eliminate the surface dipole, we propose that the superior surface properties of materials of pyrochlores are due to these extended structural features, which are a direct consequence of the inherent dipole at the surfaces