Spectroscopic signatures of the carbon buckyonions C60@C180 and C60@C240: a dispersion-corrected DFT study

Casella, Girolamo; Bagno, Alessandro; Saielli, Giacomo

doi:10.1039/c3cp53273a

Cited by 20 publications

(33 citation statements)

References 54 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In fact, it was found computationally that C60@C240 shows an UV-Vis spectrum that is the overlap of the two spectra of C60 and C240. 18 In addition, the vibrational modes of C60 and C240 in C60@C240 are clearly recognizable, with small shifts that reflect the small geometrical deformation of C60 and C240. 18 It is worth noting that the reduction in the C60 polarizability after inclusion in C240 was found to be about 75%.…”

Section: Introductionmentioning

confidence: 95%

“…Geometry relaxation of C60 and C240 in C60@C240 was found to be negligible, 19 C60 being slightly expanded inside C240, while C240 somewhat shrunk. 18 Moreover, because C60, C240, and C60@C240 are of the same symmetry (Ih), the electronic structure of these molecules is similar. In particular, their HOMO (highest occupied molecular orbital) is five-fold degenerated whereas the LUMO (lowest unoccupied molecular orbital) has three-fold degeneracy.…”

Section: Introductionmentioning

confidence: 99%

“…At the density functional theory (DFT) level, it has been found that the van der Waals interaction energy between C60 and C240 in C60@C240 is about -150 to -185 kcal/mol. [17][18][19] The global minimum of C60@C240 has D5d symmetry, although rotation of C60 inside C240 is almost free with energy barriers of about 1 kcal/mol, the Ih structure depicted in Figure 1 being almost isoenergetic with the D5d one. Geometry relaxation of C60 and C240 in C60@C240 was found to be negligible, 19 C60 being slightly expanded inside C240, while C240 somewhat shrunk.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Photoinduced Charge Separation in the Carbon Nano-Onion C₆₀@C₂₄₀

Voityuk

Solà

2016

J. Phys. Chem. A

View full text Add to dashboard Cite

The double-shell fullerene C60@C240 formed by inclusion of C60 into C240 is the smallest stable carbon nano-onion. In the paper, we analyze in detail the character of excited states of C60@C240 in terms of exciton localization and charge transfer between the inner and outer shells. The unique structure of the buckyonion leads to a large electrostatic stabilization of charge-separated (CS) states in the C60@C240. As a result, the CS states C60 + @C240-lie in the same region of the electronic spectrum (2.4-2.6 eV) as strongly absorbing locally excited states, and therefore, can be effectively populated. The CS states C60 - @C240+ are found to be by 0.5 eV higher in energy than the states C60 + @C240 -.Unlike the situation observed in donor-acceptor systems, the energy of the CS states in C60@C240does not practically depend on the environment polarity. This leads to exceptionally small reorganization energies for electron transfer between the shells. Electronic couplings for photoinduced charge separation and charge recombination processes are calculated. The absolute rate of the formation of the CS states C60 + @C240 -is estimated at ~ 4 ps -1 . The electronic features found in C60@C240 are likely to be shared by other carbon nano-onions.2

show abstract

Section: Introductionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Photoinduced Charge Separation in the Carbon Nano-Onion C₆₀@C₂₄₀

Voityuk

Solà

2016

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…In these works, the electronic structure of a confined atom was calculated explicitly, e.g., within the Hartree-Fock approximation, while the fullerene shells were modeled by a set of spherical zero-or finite-width attractive potentials. Finally, only a few works have investigated photoabsorption spectra of buckyonions [23][24][25]. Similar to pristine fullerenes, nanotubes and PAHs, photoabsorption and electron energy loss spectra of buckyonions are characterized by prominent plasmon resonances formed due to collective excitations of delocalized σ and π electrons [26,27].…”

Section: Introductionmentioning

confidence: 99%

“…These effects were explained in terms of a strong inter-fullerene coupling leading to hybridization of the electronic states of individual fullerenes and the formation of four crossover plasmons [24]. In a recent work [25], the photoabsorption spectra of C 60 @C 240 and C 60 @C 180 onions were calculated by means of time-dependent DFT (TDDFT) in the visible-near UV region (up to 5 eV). The resulting spectrum of C 60 @C 240 was characterized by a simple overlap of the spectra of isolated C 60 and C 240 because of a weak mutual perturbation of the two fullerenes upon encapsulation.…”

Section: Introductionmentioning

confidence: 99%

Photoionization of multishell fullerenes studied by ab initio and model approaches*

2016

View full text Add to dashboard Cite

Photoionization of multishell fullerenes studied by ab initio and model approaches [Eur. Phys. J. D 70 (2016) Photoionization of two buckyonions, C60@C240 and C20@C60, is investigated by means of timedependent density-functional theory (TDDFT). The TDDFT-based photoabsorption spectrum of C60@C240, calculated in a broad photon energy range, resembles the sum of spectra of the two isolated fullerenes, thus illustrating the absence of strong plasmonic coupling between the fullerenes which was proposed earlier. The calculated spectrum of the smaller buckyonion, C20@C60, differs significantly from the sum of the cross sections of the individual fullerenes because of strong geometrical distortion of the system. The contribution of collective electron excitations arising in individual fullerenes is evaluated by means of plasmon resonance approximation (PRA). An extension of the PRA formalism is presented, which allows for the study of collective electron excitations in multishell fullerenes under photon impact. An advanced analysis of photoionization of buckyonions, performed using modern computational and analytical approaches, provides valuable information on the response of complex molecular systems to the external electromagnetic field. I. INTRODUCTIONFormation and dynamics of electron excitations in fullerenes, their derivatives and other carbon-based nanoscale systems like polycyclic aromatic hydrocarbons (PAHs) have been widely studied, both experimentally and theoretically, during the past decades [1][2][3][4][5][6]. A particular attention has been paid to ionization of a C 60 fullerene under the photon, electron, and ion impact [7][8][9][10][11][12][13][14]. Because of their high symmetry and stability, these molecules have been of significant fundamental interest aimed at better understanding the photon-and chargedparticle-induced processes in complex many-particle systems. The understanding of the mechanisms of electron emission from nanoscale systems exposed to ionizing radiation is a key issue in a wide range of physical and chemical processes [15,16].Although the structure and dynamics of pristine fullerenes have been widely explored, much less attention has been paid to more complex systems, namely multishell fullerenes or buckyonions -concentric carbon nanostructures composed of several nested molecules [17,18]. Unlike fullerenes and carbon nanotubes, the properties of carbon buckyonions are still not well understood. Accurate theoretical studies of the structure and dynamical properties of these systems are also rather limited because of the large number of constituent atoms and related high computational costs.Several papers have been devoted to the study of the * verkhovtsev@iff.csic.es; On leave from A.F.

show abstract

Moving of fullerene between potential wells in the external icosahedral shell

et al. 2014

View full text Add to dashboard Cite

The results of the theoretical investigation of the behavior of fullerenes C20 and C60 inside the icosahedral external shell on example of carbon nanoclusters, C20@С240 and C60@С540, are presented in this article. The multiwell potential of interaction between fullerenes in investigated nanoclusters is calculated to reveal the regularities of moving for internal fullerene in the field of holding potential of the external shell. The possible variants of fullerenes C20 and C60 moving between the potential wells are predicted on base of topology data of the fullerenes relative positioning in nanoparticle and analysis of relief of the energy surface of interaction between fullerenes. The formulated prediction is confirmed by the data of the numerical experiment. The investigation of two-shell fullerenes allows to conclude that the light fullerene С20 will probably jump between the potential wells already at small temperatures (139-400 K) if the external shell is slightly bigger.

show abstract

Spectroscopic signatures of the carbon buckyonions C60@C180 and C60@C240: a dispersion-corrected DFT study

Cited by 20 publications

References 54 publications

Photoinduced Charge Separation in the Carbon Nano-Onion C₆₀@C₂₄₀

Photoinduced Charge Separation in the Carbon Nano-Onion C₆₀@C₂₄₀

Photoionization of multishell fullerenes studied by ab initio and model approaches*

Moving of fullerene between potential wells in the external icosahedral shell

Contact Info

Product

Resources

About

Spectroscopic signatures of the carbon buckyonions C60@C180 and C60@C240: a dispersion-corrected DFT study

Cited by 20 publications

References 54 publications

Photoinduced Charge Separation in the Carbon Nano-Onion C60@C240

Photoinduced Charge Separation in the Carbon Nano-Onion C60@C240

Photoionization of multishell fullerenes studied by ab initio and model approaches*

Moving of fullerene between potential wells in the external icosahedral shell

Contact Info

Product

Resources

About

Photoinduced Charge Separation in the Carbon Nano-Onion C₆₀@C₂₄₀

Photoinduced Charge Separation in the Carbon Nano-Onion C₆₀@C₂₄₀