First-principles investigation of thiophene adsorption on Ni13 and Zn@Ni12 nanoclusters

- Adsorption of thiophene on Zn@Ni12 clusters is calculated by DFT calculations.
- The Zn@Ni12 cluster promotes the adsorption activity of thiophene.
- There is the π-back donation in the η5 bonding modes.
- Thiophene is likely to adsorb on the Ni rather on the Zn in Ni@Ni11Zn1 cluster.

The adsorption of thiophene on icosahedral Ni13 and Zn doped Ni13 clusters is investigated using density functional theory calculations. Different adsorption possibilities have been studied. The results indicate that thiophene is preferentially adsorbed on Ni13 and Zn@Ni12 clusters with the whole ring π-bond to the hollow site (η5 bonding model). For Ni13C4H4S with η5 bonding model, the strong interaction between thiophene and Ni13 cluster results in the elongation of the SC bonds (1.78-1.83 Å) and the quite large adsorption energies (2.21-2.57 eV). However, the adsorption of thiophene with η1(S) bonding model is relatively weak based on the small value of adsorption energies (0.89 eV) and Bader charge transfer (0.07 |e|). Compared with the Ni13C4H4S clusters with η5 bonding model, the Zn@Ni12C4H4S clusters have a larger adsorption energy. When Zn atom is on the shell (Ni@Ni11Zn1), thiophene is more likely to be adsorbed on the Ni site rather on the Zn site.