Magnetic Superatoms in VLin (n = 1鈥?3) Clusters: A First-Principles Prediction

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• 作者：Meng Zhang ; Jianfei Zhang ; Xiaojuan Feng ; Hongyu Zhang ; Lixia Zhao ; Youhua Luo ; Wei Cao
• 刊名：Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：December 5, 2013
• 年：2013
• 卷：117
• 期：48
• 页码：13025-13036
• 全文大小：826K
• 年卷期：v.117,no.48(December 5, 2013)
• ISSN：1520-5215

文摘

We demonstrated a first-principles investigation to search for magnetic superatoms in the vanadium-doped lithium clusters VLi_n (n = 1鈥?3). The stabilities of VLi_n clusters were determined through geometrical and electronic optimizations. It is found that the growth pattern of VLi_n in 3-space follows adding a Li atom capped on VLi_n鈥? clusters. All doped clusters show larger relative binding energies compared with pure Li_n+1 partners and display tunable magnetic properties. When n = 8鈥?3, the VLi_n clusters adopt a cage-like structure with an endohedral V atom and are identified as superatoms with their magnetic moments successively decreasing from 5 to 0 渭_B. The isolated VLi₈ superatom is emphasized due to its robust magnetic moment as well as high structural and chemical stability analogue of a single Mn²⁺ ion. Molecular orbitals analysis shows that VLi₈ has an electronic configuration of 1S²1P⁶1D⁵, exhibiting Hund鈥檚 filling rule of maximizing the spin-like atoms. Electronic shell structures of 1S² and 1P⁶ are virtually unchanged in Li₉ cluster as the V atom substitutes for the embedded Li atom, indicating that the electron-shell-closing model is valid for explaining its structures and stabilities. The results show that the tailored magnetic building blocks for nanomaterials can be formed by seeding magnetic dopants into alkali metal cluster cages.