High-Energy Nitrogen Rings Stabilized by Superatomic Properties

How to stabilize nitrogen-rich high-energy-density molecules under conventional conditions is particularly important for the energy storage and conversion of such systems and has attracted extensive attention. In this work, the theoretical study shows for the first time that the stabilization mechanism of the nitrogen ring conforms to the superatomic properties at the atomic level. This result occurs because the stabilized anionic nitrogen rings generally exhibit planar high symmetry and the injected electrons occupy the superatomic molecular orbitals (SAMOs) of the nitrogen rings. According to these results, the typical stabilized anionic nitrogen ring structures N64-, N5-, and N42- are identified, which possess delocalized molecular orbitals with the same symmetry as the atomic orbitals and electron arrangement consistent with the electron shell arrangement of the atom. On this basis, a pathway is further designed to stabilize nitrogen rings by introducing metal atoms as electron donors to form neutral ThN6, LiN5, and MgN4 structures, thereby replacing the anionization of systems. This study highlights the importance of developing nitrogen-rich energetic materials from the perspective of superatoms. This work reports an important discovery on the stability mechanism of energetic nitrogen rings. Theoretical studies at the atomic level indicate that these common nitrogen rings form planar superatomic structures under the influence of charge transfer. Based on this, a pathway to stabilize the nitrogen ring using metal atoms as electron donors is further proposed. image