First-Principles Calculations of Magnetism in Nanoscale Carbon Materials Confining Metal with f Valence Electrons

Jiang, Wanrun; Wang, Jianpeng

doi:10.1007/s10876-015-0956-9

Cited by 9 publications

(5 citation statements)

References 99 publications

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“…The 3D nanocage structures [An@Au 14 ] n (where An = Ac, Th, Pa or U; n = −1, 0 or +1, respectively), all satisfy the 18electron configuration of 1S 2 1P 6 1D 10 jellium state that is analogous to the previously reported electronic structures such as W@Au 12 , [19] wherein the bonding involves primarily interactions between the s-and d-type shells of the endohedral atom and those of the gold-cage superatom (Au 6s orbitals). However, for the magnetic clusters (Pa@Au 14 and U@Au 14 ), these 5f-electron MOs maintain their original atomic orbital characteristics, and exhibit characteristics similar to those of the endohedral metallofullerenes (EMFs) [92][93][94] or passivated quantum dots. [95][96][97][98][99][100] The 2D planar structures, An@Au 7 (An = La or Ac), each represent a closed-shell electronic structure with a 1S 2 1P 4 1D 4 jellium model state, which is similar to previously reported structures, such as Ti@Au 6 , Sc@Cu 7 .…”

Section: Discussionmentioning

confidence: 99%

Effects of 5f-elements on electronic structures and spectroscopic properties of gold superatom model

Wang¹

2016

Chinese Phys. B

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5f-elements encaged in a gold superatomic cluster are capable of giving rise to unique optical properties due to their hyperactive valence electrons and great radial components of 5f/6d orbitals. Herein, we review our first-principles studies on electronic structures and spectroscopic properties of a series of actinide-embedded gold superatomic clusters with different dimensions. The three-dimensional (3D) and two-dimensional (2D) superatom clusters possess the 18-electron configuration of 1S 2 1P 6 1D 10 and 10-electron configuration of 1S 2 1P 4 1D 4 , respectively. Importantly, their electronic absorption spectra can also be effectively explained by the superatom orbitals. Specifically, the charge transfer (CT) transitions involved in surface-enhance Raman spectroscopy (SERS) spectra for 3D and 2D structures are both from the filled 1D orbitals, providing the enhancement factors of the order of ∼ 10 4 at 488 nm and ∼ 10 5 at 456 nm, respectively. This work implies that the superatomic orbital transitions involved in 5f-elements can not only lead to a remarkable spectroscopic performance, but also a new direction for optical design in the future.

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Section: Discussionmentioning

confidence: 99%

Effects of 5f-elements on electronic structures and spectroscopic properties of gold superatom model

Wang¹

2016

Chinese Phys. B

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“…33 Rather recent work investigated actinides in gold clusters 34 and versatile uranium−carbon nanostructure complexes. 35 So far, the only experimentally characterized (besides MS spectrum) actinide EMFs are U@C 82 and Th@C 84 , studied by Akiyama et al 8,11−13 For both the UV−vis/NIR and XANES, spectra were recorded. The XANES and electronic absorption spectra pointed out clearly that U@C 82 is U@C 82 -C 2v (9) system with uranium atom in oxidation state III.…”

Section: Introductionmentioning

confidence: 99%

“…An@C 28 , − An@C 26 , and An@C 40 series , as well as U@C 36 , Pu@C 24 , and U@C 82 have been studied theoretically. − Actinide–actinide bonding was noted by Wu and Lu in the U 2 @C 60 system in 2007, and several studies followed. − We have theoretically characterized the U 2 @C 80 molecule as a 7 U 2 @C 80 - I h (7) system where six unpaired U(5f) electrons form a double ferromagnetic bond between the enclosed uranium atoms . Rather recent work investigated actinides in gold clusters and versatile uranium–carbon nanostructure complexes …”

Section: Introductionmentioning

confidence: 99%

Properties of the Only Thorium Fullerene, Th@C₈₄, Uncovered

et al. 2017

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Only a single thorium fullerene, Th@C, has been reported to date (Akiyama, K.; et al. J. Nucl. Radiochem. Sci. 2002, 3, 151-154). Although the system was characterized by UV-vis and XANES (X-ray absorption near edge structure) spectra, its structure and properties remain unknown. In this work we used the density functional calculations to identify molecular and electronic structure of the Th@C. Series of molecular structures satisfying the ThC stoichiometric formula were studied comprising 24 IPR and 110 non-IPR Th@C isomers as well as 9 ThC@C IPR isomers. The lowest energy structure is Th@C-C(10) with the singlet ground state. Its predicted electronic absorption spectra are in agreement with the experimentally observed ones. The bonding between the cage and Th was characterized as polar covalent with Th in formal oxidation state IV. The NMR chemical shifts of Th@C-C(10) were predicted to guide the future experimental efforts in identification of this compound.

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“…Experimental studies have shown that these adsorbed defects have magnetic moments which arise from the spin polarization of adatomic electrons . Several previous studies using conventional density functional theory (DFT) have also confirmed this theoretical model …”

Section: Introductionmentioning

confidence: 63%

“…[5] Several previous studies using conventional density functional theory (DFT) have also confirmed this theoretical model. [6][7][8][9] Compared to first-principles, in particular DFT, the self-consistent charge density functional tight-binding method (SCC-DFTB, hereafter abbreviated as DFTB) provides a new extension and analysis platform for quantum calculations [10] and is aimed at giving a good approximation for DFT results. In DFTB, only the two-center integral Hamiltonian and overlap matrix elements are included, with the three-center integral neglected and a short-range repulsive potential used.…”

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confidence: 99%

The self‐consistent charge density functional tight‐binding theory study of carbon adatoms using tuned Hubbard U parameters

Wang

Dai

Jiang

et al. 2016

Int J of Quantum Chemistry

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The self‐consistent charge density functional tight‐binding (DFTB) theory is a useful tool for realizing the electronic structures of large molecular complex systems. In this study, the electronic structure of C61 formed by fullerene C60 with a carbon adatom is analyzed, using the fully localized limit and pseudo self‐interaction correction methods of DFTB to adjust the Hubbard U parameter (DFTB + U). The results show that both the methods used to adjust U can significantly reduce the molecular orbital energy of occupied states localized on the defect carbon atom and improve the gap between highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) of C61. This work will provide a methodological reference point for future DFTB calculations of the electronic structures of carbon materials.

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First-Principles Calculations of Magnetism in Nanoscale Carbon Materials Confining Metal with f Valence Electrons

Cited by 9 publications

References 99 publications

Effects of 5f-elements on electronic structures and spectroscopic properties of gold superatom model

Effects of 5f-elements on electronic structures and spectroscopic properties of gold superatom model

Properties of the Only Thorium Fullerene, Th@C₈₄, Uncovered

The self‐consistent charge density functional tight‐binding theory study of carbon adatoms using tuned Hubbard U parameters

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First-Principles Calculations of Magnetism in Nanoscale Carbon Materials Confining Metal with f Valence Electrons

Cited by 9 publications

References 99 publications

Effects of 5f-elements on electronic structures and spectroscopic properties of gold superatom model

Effects of 5f-elements on electronic structures and spectroscopic properties of gold superatom model

Properties of the Only Thorium Fullerene, Th@C84, Uncovered

The self‐consistent charge density functional tight‐binding theory study of carbon adatoms using tuned Hubbard U parameters

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Properties of the Only Thorium Fullerene, Th@C₈₄, Uncovered