Magnetic Superatoms in VLin (n = 1–13) Clusters: A First-Principles Prediction

Zhang, Meng; Zhang, Jianfei; Feng, Xiaojuan; Zhang, Hongyu; Zhao, Lixia; Luo, Yuxiang; Cao, Wei

doi:10.1021/jp410489g

Cited by 40 publications

(33 citation statements)

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“…Clearly the closed-shell electron structure is classified as a superatom that consists of specific atoms that share electrons but mimics the chemical behavior of other elements [25][26][27][28][29][30] . However, unlike previous reports of magnetic lithium superatoms that were stretched in three dimensions 31 , Li 3 O + possessed a planar structure while maintaining its superatomic properties. As shown in Fig.…”

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confidence: 80%

Evolution of lithium clusters to superatomic Li3O+

Pauna

Shi

Huttula

et al. 2017

Applied Physics Letters

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Accurate knowledge of the oxidation stages of lithium is crucially important for developing next-generation Li-air batteries. The intermediate oxidation stages, however, differ in the bulk and cluster forms of lithium. In this letter, using first-principles calculations, we predict several reaction pathways leading to the formation of Li 3 O + superatoms. Experimental results based on time-of-flight mass spectrometry and laser ablation of oxidized lithium bulk samples agreed well with our theoretical calculations. Additionally, the HOMO-LUMO gap of Li 3 O + was close to the energy released in one of these reaction paths, indicating that the superatom could act as a candidate charge-discharge unit.Keywords: Lithium-air battery, laser ablation, superatom, oxidized lithium, Li 3 O Lithium and its compounds are widely used in energy storage materials. Owing to their electrochemical properties, Li-based composites can act as both a good conductor and a semiconductor; switching of the conductivity can be realized by charging and discharging. For example semiconducting lithium peroxide 1 is composed of two equivalent lithium and oxygen atoms 2 . The formation of this compound is undesirable on the surface of lithium battery cathodes 3 ; however, Li 2 O 2 composites plays a key role in large volume Li-air batteries 3-8 . The charge-discharge pathways of Li 2 O 2 have been extensively studied in the determination of suitable battery electrolytes 3,6,8 . To further enlarge the charge-to-mass ratio of batteries, nano-and sub-nano-scale charge carriers are considered to be more capable candidates than their bulk counterparts 9,10 . In contrast to the numerous studies of Li 2 O 2 in the bulk phase, investigations of free Li-O clusters have mainly focused on hyper-lithiated Li 3 O (0,±) clusters. This set of clusters is of particular interest owing to its excess valence electrons. These clusters have been termed "superalkali atoms" in their neutral or charged forms [11][12][13][14] . Although the structure and properties of Li 3 O clusters have been systematically investigated 15 , their formation processes are not yet fully understood. Furthermore, despite many early studies on the thermochemical properties of free Li-O clusters by mass spectrometry 16 , there has been no physical characterization of lithium bulk oxidation states and those of corresponding cluster formations. As building blocks of many nanomaterials with special functionalities 17,18 , Li-based a) E-mail: henri.pauna@oulu.fi b) E-mail: mzhang@ecust.edu.cn clusters also possess unique properties, which could be applied to Li-air batteries 7 . Thus, studies of the formation mechanisms and transformations between Li-O clusters might provide new insights into future energy storage materials.In this letter we report on the evolution and transformation of free lithium clusters to superatomic Li 3 O + . The stability and reaction pathways of Li 3 O + are predicted by first-principles calculations and supported by time-of-flight mass spectrometry (TOFMS) experiments...

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confidence: 80%

Evolution of lithium clusters to superatomic Li3O+

Pauna

Shi

Huttula

et al. 2017

Applied Physics Letters

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“…1 Based on the extraordinary stability of superatoms, their optical, dielectric, magnetic, and catalytic properties have been studied in previous reports. 1,3,4 For instance, Zn@Ge 12 and Cd@Sn 12 clusters with a large HOMO-LUMO gap of about 2 eV may be used to assemble optoelectronic materials; 5 accordingly, MnCa n (n=6-15) clusters, 6 Mn@Sn 12 cluster 4,7,8 MnSr 9 cluster, 9 TcMg 8 cluster 10 and V-alkali clusters (VLi 8 , 11 VNa 8 12 and VCs 8 13 ) magnetic superatoms show a large spin magnetic moment of 5 µ B , where the superior stability of Mn@Sn 12 cluster 4,14 was confirmed in experiments. So far, it is generally accepted that the spin magnetic moment of magnetic superatoms is offered by atomic d-state electrons (or superatomic D states) localized on TM sites, while its superatomic stability is provided via the delocalized s, p-valence electrons of metal atoms fully occupied diffuse superatomic S, P states.…”

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confidence: 99%

The role of TM’s (M’s) d valence electrons in TM@X12 and M@X12 clusters

2016

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Using the density functional theory method, the icosahedral TM@X12 (M@X12) clusters (TM=Mn, Tc, Re; M=Zn, Cd, Hg; and X=Sn, Ge), which are composed of Sn12 (Ge12) shell covering a single TM (M) atom, have been systematically examined to explore the role of TM’s (M’s) d valence electrons playing in the clusters. The results show that the magnetism originate from the contribution of TM’s d valence electrons to TM@X12 clusters, where TM’s (M’s) d valence electrons are not included in the superatomic electronic states to TM@X12 (M@X12) clusters. Taking into account the structural stability (imaginary frequency, binding energy, embedding energy, and core-shell interaction) as well as the chemical stability (HOMO-LUMO gap) after, we proposed that TM@X12 and M@X12 clusters can be assigned as the protyle superatoms. Furthermore, the results suggest that M@C60 clusters can not be superatoms, because their negative embedding energies and the distance from the center atom (M) to C atom is larger than the sum of their Van Waals radii. Interestingly enough, we may obtain a simple judging method: for a magnetic superatom, the smaller the energy gap between the highest occupied magnetic state (HOMS) and Fermi level or HOMO (MOgap, or MFgap), the easier on the change of its spin magnetic moment.

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“…For a long time, the mainstream research on superatoms has been theoretical calculations and gas‐phase detection. Such studies have played a significant role in the prediction of the superatomic nature, that is, the mimicking of other elements 1–6. The key point to design superatoms is the number of valence electrons in the superatom, because the character is changed by the number of valence electrons that fill the superatomic orbitals.…”

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Superatomic Gallium Clusters in Dendrimers: Unique Rigidity and Reactivity Depending on their Atomicity

Kambe

Watanabe

et al. 2020

Advanced Materials

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Superatoms have been investigated due to their possible substitution for other elements. The solution‐phase synthesis of superatoms has attracted attention to realize the availability of superatoms. However, the previous approach is basically limited to the formation of a single cluster. Here, superatoms are investigated and the number of valence electrons in these superatoms is changed by designing the number of gallium atoms present. Based on the dendrimer template method, clusters consisting of 3, 12, 13, and other numbers of atoms have been synthesized. The halogen‐like superatomic nature of Ga13 is structurally and electrochemically observed as completely different to the other clusters. The gallium clusters of 13 and 3 atoms, which can fill the 2P and 1P superatomic orbitals, respectively, exhibit different reactivities. The 3‐atom gallium cluster is suggested as being reduced to Ga3H2− due to the lower shift of energy levels in the unoccupied orbitals. The results for these gallium clusters provide candidates for superatoms.

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Magnetic Superatoms in VLi_n (n = 1–13) Clusters: A First-Principles Prediction

Cited by 40 publications

References 83 publications

Evolution of lithium clusters to superatomic Li3O+

Evolution of lithium clusters to superatomic Li3O+

The role of TM’s (M’s) d valence electrons in TM@X12 and M@X12 clusters

Superatomic Gallium Clusters in Dendrimers: Unique Rigidity and Reactivity Depending on their Atomicity

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