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Hollow polyhedral structures and properties of Ag2n-1Sn− (n = 2–11) clusters: A theoretical study

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Abstract

Context

The structures of Ag2n-1Sn− (n = 2–11) clusters are obtained by the combination of genetic algorithm (GA) and density functional theory (DFT). All the global minimum structures prefer hollow polyhedral structures, in which S–Ag-S element, triangular Ag3S3 and tetragonal Ag4S4 units present to stabilize the structures. The S atoms in the structures appear in μ3-S or μ4-S form. Adiabatic and vertical electron affinities of the clusters have been obtained, which reveals that they increases as cluster size. Stability analysis shows that Ag9S5− and Ag19S10− have special stability. The HOMO, LUMO orbitals of the clusters are obtained and the orbital components of them are calculated. The HOMO orbitals are mainly from the p orbitals of S atoms, whereas the s, p and d orbitals of Ag atoms contribute much bigger than the p orbitals of S atoms for LUMO orbitals. The orbital delocalization indexes (ODI) of the HOMOs and LUMOs are calculated, and the small ODIs of the HOMOs and LUMOs for n = 4–10 reveal that these orbitals are highly delocalized. By studying the projected density of states and molecular orbitals of Ag9S5− and Ag19S10− clusters, it is found that their molecular orbitals have superatomic properties. Superatomic properties play an important role in stabilizing clusters.

Methods

This work used combined genetic algorithm and density functional theory (GA-DFT), and PBE0/Lanl2tz(Ag)/6-311G(d,p)(S) method to optimize the structures. Gaussian 16 program, Gauss view 6.0.16 program and Multiwfn 3.8 code are the softwares used.

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Data availability

The data set generated and analyzed during this study is included in this paper and its supplementary information file.

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Funding

This paper was supported by the teaching research project of Fuyang Normal University (2020JYXM45), research start-up fund for Dr. Zhimei Tian (2018kyqd0022) and Anhui Provincial Scientific Research Preparation Plan Project (2022AH040201).

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Authors and Affiliations

  1. School of Chemistry and Materials Engineering, Fuyang Normal University, Fuyang, 236037, Anhui, China

    Zhimei Tian, Chongfu Song, Chang Wang & Hai Wu

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  1. Zhimei Tian
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  2. Chongfu Song
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  3. Chang Wang
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  4. Hai Wu
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Contributions

All authors participated in the study. Data calculation, data analysis and figures were completed by Zhimei Tian, Chongfu Song, Chang Wang and Hai Wu. The first draft of the manuscript was written by Zhimei Tian, and all the authors commented on the previous versions of the manuscript. All authors have read and approved the final manuscript.

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Correspondence to Chongfu Song.

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Tian, Z., Song, C., Wang, C. et al. Hollow polyhedral structures and properties of Ag2n-1Sn− (n = 2–11) clusters: A theoretical study. J Mol Model 29, 105 (2023). https://doi.org/10.1007/s00894-023-05524-5

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