Geometries, stabilities, and electronic properties of small GanTi(0, ±1) (n = 1–10) clusters studied by density functional theory

• The structures of GanTi(0, ±1) clusters differ from the pure gallium clusters.
• The NP analysis show the charge transfers from gallium to titanium atoms.
• Between neutral, cationic and anion clusters show enhanced stability.
• The HOMO–LUMO gaps of GanTi cluster are distinctly higher than the Gan+1 cluster.
• The electron affinities depend sensitively on the number of Ga.

The Geometries, relative stabilities, and electronic properties of the most stable host Gan+1 and doped GanTi(0, ±1) (n = 1–10) clusters are studied using density functional theory (DFT) with valence basis set LANL2DZ. We determine the equilibrium geometries of host Gan+1 and doped GanTi(0, ±1) (n = 1–10) clusters by optimizing the bond length and bond angle of various structural isomers. With increasing cluster size, the GanTi(0, ±1) clusters tend to adopt compact structures, and the ground state structures of GanTi±1 keep the similar geometric structure as the GanTi clusters. When the number of Ga atom is even, the natural population analysis of GanTi− clusters possess high charges transfer. In order to study the stability of cluster, the average binding energies per atom (Eb/atom), fragmentation energies (Ef), second-order differences of total energies (Δ2E) of host Gan+1 and doped GanTi(0, ±1) (n = 1–10) clusters are studied. The calculation results of fragmentation energies of Gan+1 clusters present a leaping odd–even oscillatory behavior from n = 1 to n = 10. Furthermore, the calculated HOMO–LUMO gaps of GanTi clusters are distinctly higher than those of Gan+1 clusters, except for Ga3Ti clusters. The size dependence of cluster’s vertical electron detachment energies (VDE), adiabatic electron affinities (AEA), and adiabatic ionization potentials (AIP), vertical ionization potentials (VIP) are discussed.

Size dependence of the average atomic binding energies of Gan+1 and GanTi(0, ±1) (n = 1–10) clusters.Figure optionsDownload as PowerPoint slide