Structures, electronic properties and dipole magnitudes of first-row transition metal-substituted Zn₂₄S₂₄ clusters

Structures, electronic properties and dipole magnitudes of first-row transition atoms (TM)-substituted Zn24S24 clusters have been investigated by using first-principles. The Zn-S distances at the edges of the Zn24S24 and TMZn23S24 clusters become smaller than those at the centers of them. The TMZn23S24 (TM=Ti and Ni) clusters exhibit more structural stability than other clusters according to the binding energy per atom. TM substitution can obviously improve the chemical reactivity of the Zn24S24 clusters except for Sc, V and Cu by the HOMO-LUMO gap. TM (TM=Sc similar to V) atoms transfer electrons to the Zn23S24 fragments, while other TM atoms obtain electrons from the Zn23S24 fragments. The dipole magnitudes of the TMZn23S24 (TM=Ti, Ni and Cu) clusters are larger than other TMZn23S24 clusters.