Structural Evolution and Optoelectronic Properties of GaxNx Nanostructures: From Cubic to Hexagonal Configurations

In this work, the structural, electronic, optical, and vibrational properties of gallium nitride (GaxNx) nanostructures were systematically investigated using density functional theory (DFT) and time-dependent DFT (TD-DFT). A series of nanoparticles was constructed starting from a cubic-like Ga4N4 building unit, leading to one-dimensional (1D), two-dimensional (2D), three-dimensional (3D), and hexagonal configurations. Geometry optimizations and vibrational frequency calculations were performed at the B3LYP/def2-TZVP level, while optical properties were investigated using TD-DFT with the CAM-B3LYP functional. Only dynamically stable structures without imaginary vibrational frequencies were considered for spectroscopic analysis. The results reveal a strong dependence of the optical and vibrational behavior on nanoparticle size and geometry. Larger and lower-symmetry systems exhibit broader and red-shifted UV–Vis absorption spectra together with richer IR vibrational features. In contrast, elongated low-dimensional configurations such as Ga12N12–1D and Ga16N16–1D/2D were found to be dynamically unstable. The investigated nanostructures also show a clear tendency toward structural reorganization from cubic-like motifs to compact hexagonal arrangements related to the wurtzite phase of bulk GaN. Benchmark analysis demonstrates that CAM-B3LYP provides reliable excitation energies at moderate computational cost. Overall, the obtained results highlight the strong coupling between structure and optoelectronic properties in GaxNx nanostructures and indicate their potential for nanoscale optoelectronic and photonic applications.