A systematic density functional theory (DFT) and time-dependent DFT (TD-DFT) investigation of aluminum phosphide (AlxPx) nanoparticles with diverse dimensionalities and geometries is presented. Starting from a cubic-like Al4P4 building block, a series of one-dimensional (1D) elongated, two-dimensional (2D) exotic, and extended sheet-like nanostructures was constructed, enabling a unified structure–property analysis across size and topology. Optical absorption and infrared (IR) vibrational spectra were computed and correlated with geometric motifs, revealing pronounced shape-dependent tunability. Compact and highly interconnected 2D architectures exhibit red-shifted absorption and enhanced vibrational polarizability, whereas elongated or low-connectivity motifs lead to blue-shifted optical responses and stiffer vibrational frameworks. Benchmark comparisons indicate that CAM-B3LYP excitation energies closely reproduce reference EOM-CCSD trends for the lowest singlet states. Binding energy and HOMO-UMO gap analyses confirm increasing thermodynamic stability with size and dimensionality, alongside topology-driven electronic modulation. These findings establish AlP nanostructures as highly tunable platforms for optoelectronic and vibrationally active applications.
Michos et al. (Wed,) studied this question.