Searching new structures of beryllium‐doped in small‐sized magnesium clusters: Be2MgnQ (Q = 0, −1; n = 1–11) clusters DFT study

• Published in: Journal of computational chemistry Vol. 41; no. 21; pp. 1885 - 1897
• Main Authors: Zeng, Lu, Deng, Ping‐Ji, Bi, Jie, Zhu, Ben‐Chao
• Format: Journal Article
• Language: English
• Published: Hoboken, USA John Wiley & Sons, Inc 05.08.2020; Wiley Subscription Services, Inc
• Subjects: Atomic properties; Be2MgnQ (Q = 0, −1; n = 1–11); Beryllium; Calypso; Chemical bonds; Chemical composition; Clusters; Density functional theory; DFT; infrared and Raman spectra; Infrared spectra; Magnesium; Mathematical analysis; Molecular orbitals; Optimization; Raman spectra; Stability; structures
• ISSN: 0192-8651; 1096-987X
• DOI: 10.1002/jcc.26359

Using CALYPSO method to search new structures of neutral and anionic beryllium‐doped magnesium clusters followed by density functional theory (DFT) calculations, an extensive study of the structures, electronic and spectral properties of Be2MgnQ (Q = 0, −1; n = 2–11) clusters is performed. Based on the structural optimization, it is found that the Be2MgnQ (Q = 0, −1) clusters are shown by tetrahedral‐based geometries at n = 2–6 and tower‐like‐based geometries at n = 7–11. The calculations of stability indicate that Be2Mg5Q=0, Be2Mg5Q=−1, and Be2Mg8Q=−1 clusters are “magic” clusters with high stability. The NCP shows that the charges are transferred from Mg atoms to Be atoms. The s‐ and p‐orbitals interactions of Mg and Be atoms are main responsible for their NEC. In particular, chemical bond analysis including molecular orbitals (MOs) and chemical bonding composition for magic clusters to further study their stability. The results confirmed that the high stability of these clusters is due to the interactions between the Be atom and the Mg5 or Mg8 host. Finally, theoretical calculations of infrared and Raman spectra of the ground state of Be2MgnQ (Q = 0, −1; n = 1–11) clusters were performed, which will be absolutely useful for future experiments to identify these clusters. When beryllium‐doped in small size of neutral and anionic magnesium clusters, some new structures can be found. These structures of Be2MgnQ (Q = 0, −1; n = 1–11) clusters show that there are two basic structures, tetrahedral‐based (2n‐1) and tower‐like‐based (7n‐1), which can form almost all clusters structures as shown in the following figure. Obviously, the basic structures of Be2MgnQ clusters have shown a transition from simple to complex in the small size clusters. It is reasonable to believe that as the number of magnesium atoms increases, more complex and interesting structures will be found in Be2MgnQ clusters.