Trifluoromethyl-stabilized 2D nitrogen clusters: a theoretical study.

Area of Science:

• Computational Chemistry
• Materials Science
• Quantum Chemistry

Background:

• Two-dimensional (2D) all-nitrogen clusters are of interest for their potential energetic properties.
• Understanding the factors influencing the stability of these nitrogen-rich materials is crucial for their synthesis and application.

Purpose of the Study:

• To investigate the stability of 2D all-nitrogen clusters with varying numbers of nitrogen atoms (6 to 96).
• To explore the stabilizing effect of trifluoromethyl (CF₃) functional groups on these nitrogen clusters.

Main Methods:

• Utilized dispersion-corrected B3LYP functional and scaled opposite spin Møller-Plesset perturbation theory (SOS-MP2) for initial stability calculations.
• Employed domain-based local pair natural orbital coupled-cluster theory (DLPNO-CCSD(T)) for high-accuracy energy refinement of select systems.
• Analyzed the potential energy surfaces to identify stable structures and assess dynamic stability.

Main Results:

• All investigated 2D all-nitrogen clusters, functionalized with CF₃ groups, were found to be minima on their respective potential energy surfaces.
• The stability of the nitrogen clusters was observed to increase with a higher ratio of CF₃ groups to nitrogen atoms.
• While larger clusters and anion radicals exhibited dynamic instability, certain cation radicals were identified as stable minima.

Conclusions:

• Trifluoromethyl groups significantly enhance the stability of 2D all-nitrogen clusters.
• The stabilization mechanism involves favorable interactions between the lone pair orbitals of nitrogen and the antibonding sigma orbitals of the CF₃ groups.
• The findings suggest potential pathways for designing stable nitrogen-rich materials through appropriate functionalization.