Superatomic states under high pressure

Wang, Rui; Yang, Xinrui; Huang, Wanrong; Z, Liu; Zhu, Yu; Liu, Hanyu; Wang, Jianpeng

doi:10.1016/j.isci.2023.106281

Cited by 4 publications

(2 citation statements)

References 69 publications

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“…Since embedded metallofullerene has metal atoms embedded inside the fullerene cavity, its growth and stabilization mechanism are more complex and are still an unsolved mystery. Fullerene superatoms can serve as special building blocks for constructing nanomaterials due to their ability to encapsulate atoms or molecules. − In 1985, Heath et al discovered the first stable embedded metal complex, LaC 60 , which was named metallofullerene . Since then, a rich variety of endohedral metallofullerenes (EMFs) with different cage sizes and embedded atoms have been extensively studied. − Compared to larger-sized fullerenes, small fullerenes are relatively unstable due to increased curvature, causing strain within the cage and weakening π-conjugation. − Especially for the smallest fullerene C 20 , which has all pentagonal faces, the bonds tend to be sp 3 bonds rather than the sp 2 bonds that are dominant in large fullerenes .…”

Section: Introductionmentioning

confidence: 99%

Electronic Structure, Aromaticity, and Magnetism of Minimum-Sized Regular Dodecahedral Endohedral Metallofullerenes Encapsulating Rare Earth Atoms

Zhang,

Wang,

et al. 2024

ACS Omega

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A series of minimally sized regular dodecahedronembedded metallofullerene REC 20 clusters (RE = Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, and Gd) as basic units of nanoassembled materials with tunable magnetism and UV sensitivity have been explored using density functional theory (DFT). The contribution of the 4f orbital of the rare earth atom at the center of the C 20 cage to the frontier molecular orbital of REC 20 gives the REC 20 cluster additional stability. The AdNDP orbitals of the four REC 20 superatoms that conform to the spherical jellium model indicate that through natural population analysis and spin density diagrams, we observe a monotonic increase in the magnetic moment from Ce to Gd. This is attributed to the increased number of unpaired electrons in the 4f orbitals of lanthanide rare earth atoms. The UV−visible spectrum of REC20 clusters shows strong absorption in the mid-UV and near-UV bands. REC 20 clusters encapsulating lanthanide rare earth atoms stand out for their tunable magnetism, UV sensitivity, and stability, making them potential new selfassembly materials.

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Section: Introductionmentioning

confidence: 99%

Electronic Structure, Aromaticity, and Magnetism of Minimum-Sized Regular Dodecahedral Endohedral Metallofullerenes Encapsulating Rare Earth Atoms

Zhang,

Wang,

et al. 2024

ACS Omega

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“…External conditions, especially high pressure, can gradually adjust system structures and states, enabling the understanding of numerous physical mechanisms. [24][25][26][27] Therefore, as a physical tool for studying the properties of matter, including the evolution of isomerization, high pressure has garnered widespread attention. [25][26][27][28] Moreover, theoretical simulation has considerable flexibility, which can facilitate the study of compression processes in pressure and even reverse stretching procedures.…”

mentioning

confidence: 99%

Splitting of Degenerate Superatomic Molecular Orbitals Determined by Point Group Symmetry

Wang 王,

Li 李,

Liu 刘

et al. 2023

Chinese Phys. Lett.

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In this paper, we first confirm an idea obtained from first-principles calculations that is in line with symmetry theory: although superatomic molecular orbitals (SAMOs) can be classified according to their angular momentum similar to atomic orbitals, SAMOs with the same angular momentum split due to the point group symmetry of superatoms. Based on this idea, we develop a method to quantitatively modulate the splitting spacing of molecular orbitals in a superatom by changing its structural symmetry or by altering geometric parameters with the same symmetry through expansion and compression processes. Moreover, the modulation of the position crossover is achieved between the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO) originating from splitting of different angular momenta, leading to an effective reduction in system energy; this phenomenon is in line with the implication of the Jahn–Teller effect. This work provides insights into understanding and regulating the electronic structures of superatoms.

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Understanding Bonding Nature of α‐Keggin Polyoxometalates [XW₁₂O₄₀]ⁿ⁻ (X = Al, Si, P, S): A Generalized Superatomic Perspective

Li,

Shi,

et al. 2024

Energy & Environ Materials

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α‐Keggin polyoxometalates (POMs) [XW12O40]n− (X = Al, Si, P, S) are widely used in batteries owing to their remarkable redox activity. However, the mechanism underlying the applications appears inconsistent with the widely accepted covalent bonding nature. Here, first‐principles calculations show that XW12 are core–shell structures composed of a shell and an XO4n− core, both are stabilized by covalent interactions. Interestingly, owing to the presence of a substantial number of electrons in W12O36 shell, the frontier molecular orbitals of XW12 are not only strongly delocalized but also exhibit superatomic properties with high‐angular momentum electrons that do not conform to the Jellium model. Detailed analysis indicates that energetically high lying filled molecular orbitals (MOs) have reached unusually high‐angular momentum characterized by quantum number K or higher, allowing for the accommodation of numerous electrons. This attribute confers strong electron acceptor ability and redox activity to XW12. Moreover, electrons added to XW12 still occupy the K orbitals and will not cause rearrangement of the MOs, thereby maintaining the stability of these structures. Our findings highlight the structure–activity relationship and provide a direction for tailor‐made POMs with specific properties at atomic level.

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Superatomic states under high pressure

Cited by 4 publications

References 69 publications

Electronic Structure, Aromaticity, and Magnetism of Minimum-Sized Regular Dodecahedral Endohedral Metallofullerenes Encapsulating Rare Earth Atoms

Electronic Structure, Aromaticity, and Magnetism of Minimum-Sized Regular Dodecahedral Endohedral Metallofullerenes Encapsulating Rare Earth Atoms

Splitting of Degenerate Superatomic Molecular Orbitals Determined by Point Group Symmetry

Understanding Bonding Nature of α‐Keggin Polyoxometalates [XW₁₂O₄₀]ⁿ⁻ (X = Al, Si, P, S): A Generalized Superatomic Perspective

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Superatomic states under high pressure

Cited by 4 publications

References 69 publications

Electronic Structure, Aromaticity, and Magnetism of Minimum-Sized Regular Dodecahedral Endohedral Metallofullerenes Encapsulating Rare Earth Atoms

Electronic Structure, Aromaticity, and Magnetism of Minimum-Sized Regular Dodecahedral Endohedral Metallofullerenes Encapsulating Rare Earth Atoms

Splitting of Degenerate Superatomic Molecular Orbitals Determined by Point Group Symmetry

Understanding Bonding Nature of α‐Keggin Polyoxometalates [XW12O40]n− (X = Al, Si, P, S): A Generalized Superatomic Perspective

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Understanding Bonding Nature of α‐Keggin Polyoxometalates [XW₁₂O₄₀]ⁿ⁻ (X = Al, Si, P, S): A Generalized Superatomic Perspective