First-Principle Calculations of Large Fullerenes

Abstract

State of-the-art density functional theory calculations have been performed for the large fullerenes C180, C240, C320, and C540 using the linear combination of Gaussian-type orbitals density functional theory (LCGTO-DFT) approach. For the calculations all-electron basis sets were employed. All fullerene structures were fully optimized without symmetry constrains. The analysis of the obtained structures as well as a study on the evolution of the bond lengths and calculated binding energies are presented. The fullerene results are compared to diamond and graphene which were calculated at the same level of theory. This represents the first systematic study on these large fullerenes based on nonsymmetry adapted first-principle calculations, and it demonstrates the capability of DFT calculations for energy and structure computations of large scale structures without any symmetry constraint.

Structural, electronic and energetic properties of giant icosahedral fullerenes up to C6000: insights from an ab initio hybrid DFT study

“…Finally, only in recent cases the relative stability compared to the graphene sheet was investigated [19][20][21] at the ab initio level, the limiting factors being either the low level of adopted theory 19 or the small number of investigated members 20,21 .…”

Isolation of Four Isomers of C96 and Crystallographic Characterization of Nanotubular D3d(3)‐C96 and the Somewhat Flat‐Sided Sphere C2(181)‐C96

“…For example, computation efforts have focused upon predicting structural details for the series of I h fullerenes with 60, 240, 540, 960, 1500, 2160, 2940, 3840, 4860, 6000, 7260, and 8640 carbon atoms in the cage. [3][4][5] Other studies have suggested that large, empty-cage fullerenes may be unusual, low-density materials (bucky balloons). [6,7] Experimental observations of large fullerene-like structures include electron microscopic studies of carbon onions, which appear to consist of concentric shells of fullerene-like cages, [8,9] and mass spectrometric studies on electric arc generated soot, which reveal the presence of carbon clusters with even numbers of atoms up to at least C 600 .…”

Atomistic Mechanism of Carbon Nanostructure Self-Assembly as Predicted by Nonequilibrium QM/MD Simulations

“…Today, we therefore interpret the TOF-MS distribution as linear carbon chains in the region 1 Ä n < 10 [109], macrocyclic rings 10 Ä n < 30 [56,108], and fullerenes n 36 [57]. It is clear that the magic peaks at C 60 and C 70 are not the result of thermodynamic stability, since the cohesion energy of fullerenes continuously increases with the cage size approaching infinity (and thus graphite) [110,111]. Moreover, any fullerene synthesis operates under nonequilibrium conditions with a continuous energy and carbon input.…”

“…To us and others, it was puzzling that only GFs self-assembled in nonequilibrium simulations, although we already mentioned that from a thermodynamic point of view, larger fullerene cages are more stable than smaller ones [110,111] and require less curvature buildup during the cage self-assembly stage. Subsequent heating of [277].…”

“…It is clear that carbon solubility plays an important role; Ni has generally a higher C solubility than, for instance, Cu, and consequently carbide formation is well documented for Ni surfaces [235] but does not seem to play a role for Cu [251]. Temperature is equally important: Lahiri et al [252] reported low-temperature conversion of a surface carbide to graphene below 460 ı C, while at higher temperatures, carbon atoms [251] [for instance, on Cu(111) or Ni(111)], C 2 units on Rh-YSZ-Si(111) [244], or linear carbon chains [241] [on Ir (111)] attach to graphene islands. Evidence was found that graphene growth on Ni(111) [193,243], Ru(0001) [241], and Ir(111) [250] begins with carbon atoms adsorbed at step edges, while it appears that graphene islands nucleate spontaneously on terraces in case of Ir(111) [250], Rh(111) [253], and Cu(111) [251].…”