Optical and Vibrational Properties of AlN Nanoparticles with Different Geometries: A DFT and TD-DFT Study

In this work, by using density functional theory (DFT) and time-dependent DFT (TD-DFT) a comprehensive theoretical study on the structural, electronic, optical, and vibrational properties of aluminum nitride (AlxNx) nanoparticles (NPs) is presented. More than thirty nanostructures were constructed based on an initial cubic-like Al4N4 building block, including one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) configurations, as well as asymmetric and defected geometries (also known as exotic geometries). The absorption spectrum was evaluated using the CAM-B3LYP functional while geometry optimizations and vibrational frequencies were performed using the PBE functional. All calculations were performed using the triple-ζ valence plus polarization basis set def2-TZVP. The optical spectra revealed strong geometry-dependent modulation of absorption, with red-shifted and broadened UV–Vis features emerging in elongated and low-symmetry geometries. IR analysis indicates a growing number and intensity of vibrational modes with increasing dimensionality, particularly in the 300–470 cm−1 range, which corresponds to Al–N stretching and bending vibrations. Testing different exchange–correlation functionals showed that CAM-B3LYP is a good choice for excited-state calculations, matching well with the EOM-CCSD functional, which, while offering higher precision, imposes significantly higher computational requirements. Overall, the results demonstrate that structural variation in AlxNx NPs leads to tunable optoelectronic and spectroscopic behavior. These findings and calculations highlight the potential of AlN-based nanomaterials for applications in ultraviolet photonics, sensors, and future nanoscale optoelectronic devices.