Structure and Stability of Networked Metallofullerenes of the Transition Metals

Sparta, Manuel; Børve, Knut J.; Jensen, Vidar R.

doi:10.1021/jp064071h

Cited by 15 publications

(21 citation statements)

References 48 publications

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“…The mechanism of formation is believed to involve formation of a fullerenetransition metal adsorbate complex, followed by insertion into the carbon framework [104]. Additionally, the synthesis of second-and third-row transition metal-doped fullerenes has been predicted to be attainable via reaction of the corresponding transition metal trichloride (or dichloride) in the presence of chlorine gas (Cl 2 ) and buckminsterfullerene (C 60 ) [105]. Theoretical studies also provide insight into the electronic properties of transition metal-doped fullerenes [106][107][108][109].…”

Section: Introductionmentioning

confidence: 99%

Theoretical Studies of Substitutionally Doped Single-Walled Nanotubes

Yeung

Chen

Wang

2010

Journal of Nanotechnology

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The rich chemistry of single-walled carbon nanotubes (SWCNTs) is enhanced by substitutional doping, a process in which a single atom of the nanotube sidewall is replaced by a heteroatom. These so-called heteroatom-substituted SWCNTs (HSWCNTs) exhibit unique chemical and physical properties not observed in their corresponding undoped congeners. Herein, we present theoretical studies of both main group element and transition metal-doped HSWCNTs. Within density functional theory (DFT), we discuss mechanistic details of their proposed synthesis from vacancy-defected SWCNTs and describe their geometric and electronic properties. Additionally, we propose applications for these nanomaterials in nanosensing, nanoelectronics, and nanocatalysis.

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Section: Introductionmentioning

confidence: 99%

Theoretical Studies of Substitutionally Doped Single-Walled Nanotubes

Yeung

Chen

Wang

2010

Journal of Nanotechnology

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“…In other words, the stability of these compounds could depend on the degree of integration of the metal atom into the carbon network. However, significantly more stable metallofullerenes, MC 59 , are obtained for second-and third-row transition metals that are of roughly the same size as the early first-row metals (35), suggesting that the correlation between atomic radius and stability is accidental, or at least that size is not the primary cause. The variation in distortion seen between MC 59 cages of the different metals is significant ( Figure 1) and it is remarkable that this structural variation does not seem to have appreciable impact on metallofullerene stability.…”

Section: Resultsmentioning

confidence: 98%

Structure and Stability of Substitutional Metallofullerenes of the First‐Row Transition Metals

Sparta

Jensen

B⊘rve

2006

Fullerenes, Nanotubes and Carbon Nanostructures

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A DFT investigation of substitutional metallofullerenes MC 59 (M ¼ Sc-Ni) shows that they are drop-shaped, with the deviation from spherical structure depending on the size of the metal atom. The metal atomic radius, however, seems to be unimportant for the stability of the metallofullerenes. In general, the stability increases toward the right-hand side of the transition series, commensurate with the higher electronegativities of the late transition metals. CrC 59 is calculated to be more stable than the metallofullerenes of manganese and iron, suggesting that future observation of CrC 59 may be anticipated.

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“…We begin with the consideration that each Ta-Ta bond accounts for two Wannier centers ͑one for each FIG. 10. ͑Color online͒ ͑a͒ Wannier function centers around Ta site.…”

Section: Electron Localization Function and Localized Orbitalsmentioning

confidence: 99%

“…As a theoretical counterpart to experiments, density-functional theory ͑DFT͒ provides a well-suited and reliable approach to elucidate the relationship between the bonding properties of the fullerenes and the nature of the dopants. 3 However, while several studies of TM substitutional and endohedral heterofullerenes have been reported over the years, [4][5][6][7][8][9][10][11][12] the literature about the electronic structure of exohedral TM is nearly nonexistent. 11,13 The main purpose of this paper is to fill this gap by describing the electronic properties of Ta-doped exohedral heterofullerenes.…”

Section: Introductionmentioning

confidence: 99%

Electronic structure and localization properties ofC60Tanclusters(n=1

et al. 2010

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The electronic structure and the electronic localization properties of the exohedrally doped fullerene C 60 Ta, C 60 Ta 2 , and C 60 Ta 3 systems are studied in the framework of density functional theory calculations. The effect of doping the fullerene network with Ta impurities results in modifications of the Kohn-Sham energy levels spectrum in the highest occupied molecular orbital-lowest unoccupied molecular orbital ͑HOMO-LUMO͒ region and a drastic HOMO-LUMO band-gap reduction. In the vicinity of the HOMO, most of the occupied electronic states are Ta-like for C 60 Ta and C 60 Ta 2 , while C-like states or mixed C-Ta-like states are predominant for the case of C 60 Ta 3 . In all cases, we observe a conspicuous charge transfer from the Ta to the neighboring C atoms, Mulliken charges are positive on the Ta atoms and equal to 2.12 ͑C 60 Ta͒, 1.77/1.80 ͑C 60 Ta 2 ͒, and 1.61/1.62 ͑C 60 Ta 3 ͒. The values of the valence charges on the Ta atoms reflect their coordination environment and are the largest in C 60 Ta 3 ͑3.00/3.25͒. This is compatible with the existence of three nearest neighbors ͑two Ta and one C͒ for each one of the Ta atoms in C 60 Ta 3 . We provide an insight into the physical nature of bonding by means of an accurate electronic structure analysis in terms of the electron localization function and the maximally localized Wannier orbitals. Among the Ta valence electrons, the most localized ones are those not involved in bond formation, charge transfer effects concurring to the establishment of ionic-covalent bonds between the Ta and the neighboring C atoms.

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Structure and Stability of Networked Metallofullerenes of the Transition Metals

Cited by 15 publications

References 48 publications

Theoretical Studies of Substitutionally Doped Single-Walled Nanotubes

Theoretical Studies of Substitutionally Doped Single-Walled Nanotubes

Structure and Stability of Substitutional Metallofullerenes of the First‐Row Transition Metals

Electronic structure and localization properties ofC60Tanclusters(n=1

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