LAUSR

Abstract A series of nanostructures of Zinc Sulfide (ZnS), including the small Zn n S n ( n  = 1–15) clusters, the magic cage-like Zn 12 S 12 and its derivants (Zn 12 S 12 -based dimers, trimers, nanowires and monolayer) were systematically investigated by using a first-principles bottom-up calculation. The results show that the Zn 12 S 12 cage-like structure with six isolated four-membered rings (4NRs) and eight six-membered rings (6NRs) has T h symmetry and a large HOMO-LUMO gap, indicating that the Zn 12 S 12 cluster would be ideal building blocks for the synthesis of new cluster-assembled materials. Via the aggregation of Zn 12 S 12 , we find that the Zn 12 S 12 cages can bind into various porous materials with different dimensionality by the most stable bonding H H 1 . Interestingly, all of these cluster-assembled structures are found to be more stable than the individual Zn 12 S 12 cage and rock salt (RS) phase of ZnS. These fascinating findings will be advantageous for promoting the potential applications of the inorganic ZnS-based nanosystems in the new type of electronic nanodevices and high-performance semiconductor materials.