Theoretical study on prismatic (N₆)_n (n=16-35) molecules

Area of Science:

• Computational Chemistry
• Materials Science
• Nanotechnology

Background:

• Previous studies investigated the stability of pure nitrogen molecules.
• Understanding the stability of nitrogen allotropes is crucial for novel material development.

Purpose of the Study:

• To investigate the structures and energies of (N6)n molecular sequences (n=16-35).
• To analyze the bonding properties and electronic topologies of these prismatic nitrogen molecules.
• To elucidate the mechanism of van der Waals force generation in stabilizing these structures.

Main Methods:

• Density Functional Theory (DFT) calculations using B3LYP/cc-pvDZ.
• Natural Bond Orbital (NBO) analysis for bonding properties.
• Atoms in Molecule (AIM) analysis for electronic topologies.

Main Results:

• Van der Waals forces are identified as the dominant stabilizing factor for large prismatic nitrogen cages.
• A dense network of interweaving van der Waals and covalent bonds tightly binds nitrogen atoms.
• Van der Waals forces originate from atom-atom proximity and partial sp3 orbital overlap between specific nitrogen atoms on the hexagonal surfaces.

Conclusions:

• Prismatic (N6)n molecules are stabilized by a unique interplay of covalent and van der Waals interactions.
• These structures exhibit potential as novel, environmentally friendly nitrogen nanotubes or nanofibers.
• The findings open prospects for the study and application of nitrogen-based nanomaterials.