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Structural stability and evolution of terbium‐doped silicon clusters and influence of 4 f → 5 d electronic transition mechanism on magnetism and appearance of photoelectron spectroscopy for TbSi n 0/− ( n = 6‐18) clusters
Author(s) -
Gu Yansong,
Yang Jucai,
Cheng Lin
Publication year - 2020
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26087
Subject(s) - terbium , x ray photoelectron spectroscopy , chemistry , cluster (spacecraft) , magnetism , atom (system on chip) , crystallography , electronic structure , density functional theory , electron configuration , chemical shift , atomic physics , computational chemistry , nuclear magnetic resonance , physics , condensed matter physics , ion , organic chemistry , computer science , embedded system , programming language
The global minimal structures of terbium‐doped Si clusters and their anions TbSi n 0/− ( n = 6‐18) are confirmed by employing the ABCluster unbiased global search technique combined with a B2PLYP double‐hybrid density functional and comparing consistency of simulated and experimental photoelectron spectroscopy (PES). The results demonstrated that structural evolution patterns for neutral clusters prefer Tb‐substitutional to Tb‐encapsulated configuration starting from n = 16. While for the corresponding anionic clusters, the growth pattern adopts Tb‐linked structures to encapsulated motif. The Natural Population Analysis revealed that the 4 f electrons of Tb atom in TbSi n 0/− ( n = 6‐18) clusters participate in bonding. The way to participate in bonding is one 4 f electron transition to 5 d orbital ([Xe]6 s 2 4 f 9 → [Xe]6 s 2 4 f 8 5 d 1 ), which significantly affects the cluster's magnetism and appearance of PES. The total magnetic moments of neutral TbSi n and the corresponding anions maintain at 7 μB and 6 μB, respectively, which are larger than that of an isolated Tb atom. The HOMO‐LUMO energy gap, relative stability, and chemical bonding analysis demonstrated that superatomic TbSi 16 − cluster is a magic cluster with fine thermodynamic and moderate chemical stability.