Structure and electronic properties of [AunV]λ (n = 1–9; λ = 0, ± 1) nanoalloy clusters within density functional theory framework

The structure and physico-chemical properties of vanadium-doped gold nanoalloy clusters [AunV]λ (n = 1–9; λ = 0, ± 1) are reported within density functional theory framework. The ground state configurations reveal that neutral and anionic clusters favour planar structures for n = 1–9, whereas cationic clusters show three-dimensional geometries for n = 7–9. Our computed results show that the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) energy gap of neutral, cationic and anionic nanoalloy clusters is in the range of 1.41 eV to 2.50 eV, 1.04 eV to 2.37 eV and 1.25 eV to 2.24 eV, respectively. It justifies the applications of [AunV] clusters in optoelectronic, photovoltaic and nonlinear optical devices. The HOMO–LUMO energy gap and molecular hardness reveal a fascinating odd–even alteration as a function of cluster size. The electronegativity, electrophilicity index and dipole moment of cationic clusters are more as compared to neutral and anionic clusters. The computed dipole polarizability has a linear relationship with the cluster size. Calculated bond length, dissociation energy and vibrational frequency for species [Au2]λ and [AuV]λ (λ = 0, ± 1) are in agreement with the experimental results.