The structures and stabilities of gold clusters with up to 14 atoms have been determined by density-functional theory. The structure optimizations and frequency analysis are performed with the Perdew-Wang 1991 gradient-corrected functional combined with the effective core potential and corresponding valence basis set (LANL2DZ). The turnover point from two-dimensional to three-dimensional geometry for gold clusters occurs at Au12. The energetic and electronic properties of the small gold clusters are strongly dependent on sizes and structures, which are in good agreement with experiment and other theoretical calculations. The even-odd oscillation in cluster stability and electronic properties predicted that the clusters with even numbers of atoms were more stable than the neighboring clusters with odd numbers of atoms. The stability and electronic structure properties of gold clusters are also characterized by the maximum hardness principle of chemical reactivity and minimum polarizability principle.

Morphology management for tailoring the properties of monolayer transition-metal dichalcogenides (TMDCs), that is, molybdenum disulfide (MoS), has attracted great interest for promising applications such as in electrocatalysis and optoelectronics. Nevertheless, little progress has been made in engineering the shape of MoS. Herein, we introduce a modified chemical vapor deposition method to grow monolayer MoS dendrites by pretreating substrates with adhesive tapes. The as-grown MoS crystals are featured with hexagonal backbones with fractal shapes and tunable degrees. By characterizing the atomic structure, it is found that these morphologies are mainly initiated from the twin defect derived growth and controlled by the S:Mo vapor ratio. Due to the accumulated sulfur vacancies in the cyclic twin regions, strong enhancement of photoluminescence emission is localized, which determines the shape dependency of optical property. This work not only enriches the understanding of the twin defects derived crystal growth mechanism and extends its applications from nanomaterials to two-dimensional crystals, but also offers a robust and controllable protocol for shape-engineered monolayer TMDCs in electrochemical and optoelectronic applications.

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