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Sample records for entire c-60 molecule

  1. Electrostatic propulsion using C60 molecules

    NASA Technical Reports Server (NTRS)

    Leifer, Stephanie D.; Rapp, Donald; Saunders, Winston A.

    1992-01-01

    An evaluation is made of the potential benefits of C60 molecules as a basis for ion propulsion. Because C60 is storable, its use may result in a larger usable propellant fraction than previous methods of cluster ion propulsion. C60 may also relax such engineering constraints as grid spacing, which restrict the performance of noble gas ion propulsion. The behavior of C60 in a plasma discharge environment, as well as various electron impact cross sections of the molecule, will greatly afftect the feasibility of the concept.

  2. Electrostatic Propulsion Using C60 Molecules

    NASA Technical Reports Server (NTRS)

    Leifer, Stephanie D.; Saunders, Winston A.

    1993-01-01

    Report proposes use of C60 as propellant material in electrostatic propulsion system of spacecraft. C60, C70, and similar molecules, have recently been found to have characteristics proving advantageous in electrostatic propulsion. Report discusses these characteristics and proposes experiments to determine feasibility of concept.

  3. "Soft" metallic contact to isolated C60 molecules.

    PubMed

    Glowatzki, Hendrik; Bröker, Benjamin; Blum, Ralf-Peter; Hofmann, Oliver T; Vollmer, Antje; Rieger, Ralph; Müllen, Klaus; Zojer, Egbert; Rabe, Jürgen P; Koch, Norbert

    2008-11-01

    C60 adsorbed on a monolayer of hexaazatriphenylene-hexanitrile (HATCN) on Ag(111) is investigated by ultraviolet photoelectron spectroscopy (UPS) and scanning tunneling microscopy. UPS and quantum-mechanical modeling show that HATCN chemisorbed on Ag(111) displays metallic character. This metallic molecular layer decouples C60 electronically from the Ag substrate and simultaneously acts both as template for the stable adsorption of isolated C60 molecules at room temperature and as "soft" metallic contact for subsequently deposited molecules. PMID:18954123

  4. Vibration-rotation spectroscopy of molecules trapped inside C60.

    PubMed

    Cross, R James

    2008-08-01

    A simple model is developed to treat the energy levels and spectroscopy of diatomic molecules inside C 60. The C 60 cage is treated as spherically symmetric, and the coupling to the C 60 vibrations is ignored. The remaining six degrees of freedom correspond to the vibrations and rotations of the diatomic molecule and the rattling vibration of the molecule inside the cage. By using conservation of angular momentum, we can remove two of these motions and simplify the calculations. The resulting energy levels are simple and can be labeled by a set of quantum numbers. The IR and Raman spectra look like those of gas-phase diatomic molecules at low temperatures. At higher temperatures, hot bands due to the low-frequency rattling mode appear, and the spectrum becomes congested, looking like a solution spectrum. PMID:18598014

  5. Effective medium theory for a system of C60 molecules

    NASA Astrophysics Data System (ADS)

    Moradi, Afshin

    2016-06-01

    An effective medium theory is developed to study the effective permittivity of a system of C60 molecules. We use a two-dimensional, spherical, two-fluid hydrodynamic model to describe the linear response of the π and σ electrons over the each C60 molecule. A general expression for the electromagnetic wave attenuation coefficient of the system is then deduced, and its functional dependence on the filling factor is presented. Furthermore, the dispersion characteristics of electromagnetic oscillations of the system are studied.

  6. Structure and dynamics of C60 molecules on Au(111)

    SciTech Connect

    Shin, Heekeun; Schwarze, A; Diehl, R D; Pussi, K; Colombier, A; Gaudry, E.; Ledieu, J; McGuirk, G M; Serkovic Loli, L N; Fournee, V; Wang, Lin-Lin; Schull, G; Berndt, R

    2014-06-01

    Earlier studies of C60 adsorption on Au(111) reported many interesting and complex features. We have performed coordinated low-energy electron diffraction, scanning tunneling microscopy (STM), and density functional theory studies to elucidate some of the details of the monolayer commensurate (2√3 × 2√3)R30° phase. We have identified the adsorption geometries of the two states that image as dim and bright in STM. These consist of a C60 molecule with a hexagon side down in a vacancy (hex-vac) and a C60 molecule with a carbon-carbon 6:6 bond down on a top site (6:6-top), respectively. We have studied the detailed geometries of these states and find that there is little distortion of the C60 molecules, but there is a rearrangement of the substrate near the C60 molecules. The two types of molecules differ in height, by about 0.7 Å, which accounts for most of the difference in their contrast in the STM images. The monolayer displays dynamical behavior, in which the molecules flip from bright to dim, and vice versa. We interpret this flipping as the result of the diffusion of vacancies in the surface layers of the substrate. Our measurements of the dynamics of this flipping from one state to the other indicate that the activation energy is 0.66 ± 0.03 eV for flips that involve nearest-neighbor C60 molecules, and 0.93 ± 0.03 for more distant flips. Based on calculated activation energies for vacancies diffusing in Au, we interpret these to be a result of surface vacancy diffusion and bulk vacancy diffusion. These results are compared to the similar system of Ag(111)-(2√3 × 2√3)R30°-C60. In both systems, the formation of the commensurate C60 monolayer produces a large number of vacancies in the top substrate layer that are highly mobile, effectively melting the interfacial metal layer at temperatures well below their normal melting temperatures.

  7. Gate-tunable large negative tunnel magnetoresistance in Ni-C60-Ni single molecule transistors.

    PubMed

    Yoshida, Kenji; Hamada, Ikutaro; Sakata, Shuichi; Umeno, Akinori; Tsukada, Masaru; Hirakawa, Kazuhiko

    2013-02-13

    We have fabricated single C(60) molecule transistors with ferromagnetic Ni leads (FM-SMTs) by using an electrical break junction method and investigated their magnetotransport. The FM-SMTs exhibited clear gate-dependent hysteretic tunnel magnetoresistance (TMR) and the TMR values reached as high as -80%. The polarity of the TMR was found to be always negative over the entire bias range studied here. Density functional theory calculations show that hybridization between the Ni substrate states and the C(60) molecular orbitals generates an antiferromagnetic configuration in the local density of states near the Fermi level, which gives a reasonable explanation for the observed negative TMR. PMID:23327475

  8. Jellium model potentials for the C60 molecule and the photoionization of endohedral atoms, A@C60

    NASA Astrophysics Data System (ADS)

    Baltenkov, A. S.; Manson, S. T.; Msezane, A. Z.

    2015-09-01

    Approximating the C60 shell as a collection of carbon atoms, the potential experienced by a confined atom has been calculated within the framework of the self-consistent spherical jellium model. It has been found that the potential well in this model has a cusp-shaped Lorentz-like profile. The parameters of the model Lorentz-bubble potential (depth and thickness) have been selected so that in the potential well there would be an electronic level corresponding to the experimental electron affinity of the C60 molecule. The spatial distribution of the positive charge of the C-atomic nuclei and the negative charge of the electron clouds forming the electrostatic potential of C60, as a whole, has been analyzed using the Poisson equation. It is demonstrated that the often used radial square-well potential to approximate the C60 corresponds to a non-physical charge density for the C60 molecule. This analysis demonstrates that the phenomenological potentials simulating the C60 shell potential should belong to a family of potentials with a non-flat bottom and non-parallel potential walls similar to the Lorentz-bubble potential. The photoionization cross-sections of a hydrogen atom localized at the center of the C60 shell have been calculated as well. It is found that confinement oscillations in the cross-sections are exhibited within the framework of the cusp-shaped potential model and these oscillations are essentially the same as those in the case of the potential wells with well-defined borders (parallel walls), thereby demonstrating that the inherent characteristic distances of the potential, e.g., radii of the potential walls, or the distances between potential walls, are not necessary to produce confinement resonances; this should be a general result for atoms or molecules confined in near-spherical fullerenes.

  9. C60 molecules grown on a Si-supported nanoporous supramolecular network: a DFT study.

    PubMed

    Boukari, Khaoula; Duverger, Eric; Stephan, Régis; Hanf, Marie-Christine; Sonnet, Philippe

    2014-07-28

    C60 fullerene assemblies on surfaces have attracted considerable attention because of their remarkable electronic properties. Now because of the competition between the molecules-substrate and the molecule-molecule interactions, an ordered C60 array is rather difficult to obtain on silicon surfaces. Here we present density functional theory simulations on C60 molecules deposited on a TBB (1,3,5-tri(1'-bromophenyl)benzene) monolayer lying on the Si(111)-boron surface (denoted SiB). The C60 molecules are located in the nanopores formed by the TBB network. Adsorption energy calculations show that the SiB surface governs the C60 vertical position, whereas the TBB network imposes the C60 lateral position, and stabilizes the molecule as well. The low charge density between the C60 and the SiB substrate on one hand, and on the other hand between the C60 and the TBB molecules, indicates that no covalent bond is formed between the C60 and its environment. However, according to charge density differences, a drastic charge reorganisation takes place between the Si adatoms and the C60 molecule, but also between the C60 and the surrounding TBB molecules. Finally, calculations show that a C60 array sandwiched between two TBB molecular layers is stable, which opens up the way to the growth of 3D supramolecular networks. PMID:24920165

  10. Energetics and Electronic Structures of C60 Included Within [n]Cyclacene Molecules

    NASA Astrophysics Data System (ADS)

    Kigure, Shota; Okada, Susumu

    2013-09-01

    We report the geometric and electronic structures of C60 included within cyclic hydrocarbon molecules, i.e., [n]cyclacene molecules. We found that the C60 included within the [n]cyclacene molecules ([n]cyclacene\\supsetC60) are energetically stable and that the inclusion reactions are exothermic for the [n]cyclacene molecules where n is larger than 16. Because of quantum confinement of the electronic states of the guest C60 molecule by the host [n]cyclacene, the electronic structure of [n]cyclacene\\supsetC60 is complex. The energy gap between the highest occupied states and the lowest unoccupied states is opened between the electronic states of the guest and host molecules.

  11. Spatially mapping the spectral density of a single C60 molecule

    SciTech Connect

    Lu, Xinghua; Grobis, M.; Khoo, K.H.; Louie, Steve G.; Crommie, M.F.

    2002-07-01

    We have used scanning tunneling spectroscopy to spatially map the energy-resolved local density of states of individual C60 molecules on the Ag(100) surface. Spectral maps were obtained for molecular states derived from the C60 HOMO, LUMO, and LUMO + 1 orbitals, revealing new details of the spatially inhomogeneous C60 local electronic structure. Spatial inhomogeneities are explained using ab initio pseudopotential density functional calculations. These calculations emphasize the need for explicitly including the C60-Ag interaction and STM tip trajectory to understand the observed C60 local electronic structure.

  12. STM study of C60F18 high dipole moment molecules on Au(111)

    NASA Astrophysics Data System (ADS)

    Bairagi, K.; Bellec, A.; Chumakov, R. G.; Menshikov, K. A.; Lagoute, J.; Chacon, C.; Girard, Y.; Rousset, S.; Repain, V.; Lebedev, A. M.; Sukhanov, L. P.; Svechnikov, N. Yu.; Stankevich, V. G.

    2015-11-01

    Scanning tunneling microscopy and spectroscopy studies of C60F18 molecules deposited on Au(111) are reported and compared to C60 molecules both at liquid helium temperature and room temperature (RT). Whereas adsorption and electronic properties of C60F18 single molecules were studied at low temperature (LT), self-assemblies were investigated at RT. In both cases, the fluorine atoms of the C60F18 molecules are pointed towards the surface. Individual C60F18 molecules on Au(111) have a HOMO-LUMO gap of 2.9 eV. The self-assembled islands exhibit a close-packed hexagonal lattice with amorphous borders. The comparison with C60 molecules clearly demonstrates the influence of the C60F18 electric dipole moment (EDM) on the electronic properties of single molecules and on the thermodynamics of self-assembled islands. Besides, the apparent height value of a separate molecule increases in a self-assembly environment as a result of a depolarization phenomenon.

  13. Transport characteristics of a single C60-molecule junction revealed by multiple Andreev reflections

    NASA Astrophysics Data System (ADS)

    Hiraoka, Ryoichi; Arafune, Ryuichi; Tsukahara, Noriyuki; Kawai, Maki; Takagi, Noriaki

    2014-12-01

    We have determined the number of transport channels and the value of the transmission coefficients of a single molecular junction by measuring the multiple Andreev reflections (MARs) with a scanning tunneling microscope (STM). By precisely positioning a Nb STM tip to a single C60 molecule on Pb(111), a single molecular junction was fabricated in which the C60 molecule connects with the two superconducting electrodes. From the subharmonic gap structures arising from MARs in the current-voltage characteristics together with the tunneling spectrum of the C60 molecule, we found that unoccupied molecular orbitals of C60 extending to the Fermi level provide three electronic transport channels in the molecular junction. We also found that the transmission coefficients depend on the contact geometry of the molecule. These results demonstrate that the combination of the STM imaging with the MARs measurement provides an effective path for investigating the electronic transport properties through a single molecule sandwiched by two superconducting electrodes.

  14. Theoretical study of the charge transport through C60-based single-molecule junctions

    NASA Astrophysics Data System (ADS)

    Bilan, S.; Zotti, L. A.; Pauly, F.; Cuevas, J. C.

    2012-05-01

    We present a theoretical study of the conductance and thermopower of single-molecule junctions based on C60 and C60-terminated molecules. We first analyze the transport properties of gold-C60-gold junctions and show that these junctions can be highly conductive (with conductances above 0.1G0, where G0=2e2/h is the quantum of conductance). Moreover, we find that the thermopower in these junctions is negative due to the fact that the lowest unoccupied molecular orbital dominates the charge transport, and its magnitude can reach several tens of microvolts per kelvin, depending on the contact geometry. On the other hand, we study the suitability of C60 as an anchoring group in single-molecule junctions. For this purpose, we analyze the transport through several dumbbell derivatives using C60 as anchors, and we compare the results with those obtained with thiol and amine groups. Our results show that the conductance of C60-terminated molecules is rather sensitive to the binding geometry. Moreover, the conductance of the molecules is typically reduced by the presence of the C60 anchors, which in turn makes the junctions more sensitive to the functionalization of the molecular core with appropriate side groups.

  15. Short-pulse laser-produced plasma from C60 molecules

    SciTech Connect

    Wuelker, Cornelius; Theobald, Wolfgang; Ouw, Donald; Schaefer, Fritz P.; Chichkov, Boris N.

    1995-05-01

    The first experimental observations of a plasma produced in a vapor of C60 molecules with a high-intensity subpicosecond KrF laser (6x10{sup 15} W/cm{sup 2}) are reported. It differs from a plasma created in an ordinary carbon preplasma by reaching much higher ionization stages under the same experimental conditions. This remarkable property of C60 molecules (and other clusters) opens new prospects for short-pulse driven X-ray lasers.

  16. The Adsorption of C60 fullerene molecules on Nanostructured Au (111)

    NASA Astrophysics Data System (ADS)

    Zhang, Xin; Guo, Quanmin; Palmer, Richard

    2009-03-01

    The sub-monolayer growth of C60 molecules on the Au (111) surface has been studied using STM in ultra high vacuum. The C60 molecules tend to form close-packed layers due to a strong inter-molecular interaction. However, within the close-packed layer, there are finer, secondary structures that are specific to each of all the three C60/Au interfacial structures ((23x23)R30 , in-phase (R0 ) and R14 ) observed [1]. This is a consequence of the molecule-substrate interaction and our findings demonstrate a much more complex structural variation at the molecule-substrate interface than previously assumed. Furthermore, within the R14 C60 layer, slightly darker molecules (30 pm lower) aligned along the ã11-2õdirection with a ˜6 nm spacing are observed and these molecules are arranged in a reasonably well-ordered two-dimensional lattice. C60 molecules are also found to decorate the elbow sites of the herringbone reconstructed Au(111) even at room, and when fullerenes are deposited to arrays of fabricated monolayer gold stripes (gold-fingers) [2], the molecules show step-specific attachment where the step edges with the (111) micro-facet are preferentially populated.[0pt] [1] X. Zhang, F. Yin, R. E. Palmer and Q. Guo, Surf. Sci. 602 (2008) 885-892.[0pt] [2] Q. Guo, F. Yin and R. E. Palmer, Small 1 (2005) 76-79.

  17. Alignment of paired molecules of C60 within a hexagonal platform networked through hydrogen-bonds.

    PubMed

    Hisaki, Ichiro; Nakagawa, Shoichi; Sato, Hiroyasu; Tohnai, Norimitsu

    2016-07-28

    We demonstrate, for the first time, that a hydrogen-bonded low-density organic framework can be applied as a platform to achieve periodic alignment of paired molecules of C60, which is the smallest example of a finite-numbered cluster of C60. The framework is a layered assembly of a hydrogen-bonded 2D hexagonal network (LA-H-HexNet) composed of dodecadehydrotribenzo[18]annulene derivatives. PMID:27417325

  18. Direct Observation of a Gas Molecule (H2, Ar) Swallowed by C60

    SciTech Connect

    Sawa, H.; Kakiuchi, T.; Wakabayashi, Y.; Murata, Y.; Murata, M.; Komatsu, K.; Yakigaya, K.; Takagi, H.; Dragoe, N.

    2007-01-19

    Various types of endohedral fullerene complexes are known to date. The well known metallofullerenes are generally produced by arc-discharge method, but the use of such extremely drastic conditions is apparently not suitable for encapsulation of unstable molecules or gases. We recently succeeded in incorporation of a H2 molecule or an Ar atom in 100% into a C60. In order to observe the endohedral gas molecule directly, the X-ray diffraction analysis using synchrotron radiation were carried out. We observed a gas molecule encapsulated in each fullerene cage using structure analysis and the maximum entropy method. These gas molecules are floating inside of the hollow cavities and are completely isolated from the outside.

  19. Self-interaction corrections applied to Mg-porphyrin, C60, and pentacene molecules

    NASA Astrophysics Data System (ADS)

    Pederson, Mark R.; Baruah, Tunna; Kao, Der-you; Basurto, Luis

    2016-04-01

    We have applied a recently developed method to incorporate the self-interaction correction through Fermi orbitals to Mg-porphyrin, C60, and pentacene molecules. The Fermi-Löwdin orbitals are localized and unitarily invariant to the Kohn-Sham orbitals from which they are constructed. The self-interaction-corrected energy is obtained variationally leading to an optimum set of Fermi-Löwdin orbitals (orthonormalized Fermi orbitals) that gives the minimum energy. A Fermi orbital, by definition, is dependent on a certain point which is referred to as the descriptor position. The degree to which the initial choice of descriptor positions influences the variational approach to the minimum and the complexity of the energy landscape as a function of Fermi-orbital descriptors is examined in detail for Mg-porphyrin. The applications presented here also demonstrate that the method can be applied to larger molecular systems containing a few hundred electrons. The atomization energy of the C60 molecule within the Fermi-Löwdin-orbital self-interaction-correction approach is significantly improved compared to local density approximation in the Perdew-Wang 92 functional and generalized gradient approximation of Perdew-Burke-Ernzerhof functionals. The eigenvalues of the highest occupied molecular orbitals show qualitative improvement.

  20. Self-interaction corrections applied to Mg-porphyrin, C60, and pentacene molecules.

    PubMed

    Pederson, Mark R; Baruah, Tunna; Kao, Der-You; Basurto, Luis

    2016-04-28

    We have applied a recently developed method to incorporate the self-interaction correction through Fermi orbitals to Mg-porphyrin, C60, and pentacene molecules. The Fermi-Löwdin orbitals are localized and unitarily invariant to the Kohn-Sham orbitals from which they are constructed. The self-interaction-corrected energy is obtained variationally leading to an optimum set of Fermi-Löwdin orbitals (orthonormalized Fermi orbitals) that gives the minimum energy. A Fermi orbital, by definition, is dependent on a certain point which is referred to as the descriptor position. The degree to which the initial choice of descriptor positions influences the variational approach to the minimum and the complexity of the energy landscape as a function of Fermi-orbital descriptors is examined in detail for Mg-porphyrin. The applications presented here also demonstrate that the method can be applied to larger molecular systems containing a few hundred electrons. The atomization energy of the C60 molecule within the Fermi-Löwdin-orbital self-interaction-correction approach is significantly improved compared to local density approximation in the Perdew-Wang 92 functional and generalized gradient approximation of Perdew-Burke-Ernzerhof functionals. The eigenvalues of the highest occupied molecular orbitals show qualitative improvement. PMID:27131541

  1. Peas in a pod: quasi-one-dimensional C60 molecules in a nanotube

    NASA Astrophysics Data System (ADS)

    Gatica, Silvina M.; Mercedes Calbi, M.; Cole, Milton W.

    2003-03-01

    We evaluate the equation of state of the quasi-one-dimensional phase of C60 molecules in small carbon nanotubes, nicknamed "peas in a pod"[1,2]. The pressure and chemical potential are evaluated as functions of the temperature and density, within the approximation of nearest neighbor interactions and classical statistical mechanics. A phase transition to a 3D anisotropic condensed phase is predicted as a result of the interaction between molecules in adjacent tubes. [1] B.W. Smith, M. Monthioux and D.E. Luzzi, Nature 296, 323 (1998). [2] M. Hodak, L.A. Girifalco, Phys. Rev. B 64, 035407 (2001), Chem. Phys. Lett. 350, 405 (2001); L.A. Girifalco and M. Hodak, App. Phys. A, in press.

  2. Specific features of the glass transition in C60 fullerite saturated with carbon monoxide molecules: Photoluminescence studies

    NASA Astrophysics Data System (ADS)

    Zinoviev, P. V.; Zoryansky, V. N.; Stetsenko, Yu. E.; Danchuk, V. V.

    2016-02-01

    Low temperature (20-230 K) spectral-luminescence studies were conducted on C60 fullerite saturated with carbon monoxide in a physisorption regime. Substantial changes in the photoluminescence characteristics of C60-CO solutions with different impurity concentrations were found already for short intercalation times. Strong dependence of the CO solubility on the saturation temperature was revealed by analyzing the contribution of "deep X-traps" to the luminescence. Furthermore, it was found that filling of the octahedral voids by CO molecules occurs with a lower gradient of the impurity distribution into the bulk C60 crystals as compared with N2. The temperature dependences of the integral emission intensity for the samples with different concentrations of carbon monoxide were studied. For the first time, using the spectral-luminescence method, it was revealed that CO molecules, in contrast to H2 and N2, exhibit a significant effect on the formation of the orientational glass and the rotational dynamics of C60 molecules. Within the model of the transfer of electronic excitation in C60 crystals, the effect of polar CO molecules on the reorientation of C60 molecules and the change in the nature of their rotation in concentrated C60-CO solutions, leading to the observed strong shift of the temperatures of orientational Tc and glass Tg transitions to lower temperatures accompanied by "blurring" of the transition boundaries, were explained.

  3. Trap states in ZnPc:C60 small-molecule organic solar cells

    NASA Astrophysics Data System (ADS)

    Burtone, Lorenzo; Fischer, Janine; Leo, Karl; Riede, Moritz

    2013-01-01

    Trap states are known to be one of the key parameters limiting charge transport in organic semiconductors and hence the performance of organic solar cells. Here, small-molecule organic solar cells based on a bulk heterojunction between zinc-phtalocyanine (ZnPc) and the fullerene C60 are characterized according to their trapping nature by noninvasive methods and under ambient conditions. We show how impedance spectroscopy, applied to systematically varied device structures, reveals the trap localization as well as its occupation mechanisms. Further insight is given from investigations of different device working points and illumination intensities. Thus, we find the traps to be bulk states in the active layer with an electron-trapping nature. They can be described by a Gaussian energy distribution of 55 meV width, centered at 0.46 eV below the electron transport level and with a concentration of 3.5 × 1016 cm-3. Moreover, the trap states act as recombination centers in the presence of injected or photogenerated charge carriers. The results are confirmed by electrical simulations.

  4. Rotations and vibrations of water molecule inside the fullerene cage: infrared study of H2O@C60

    NASA Astrophysics Data System (ADS)

    Room, Toomas; Shugai, A.; Nagel, U.; Mamone, S.; Krachmalnicoff, A.; Whitby, R. J.; Levitt, M. H.; Nishida, T.; Murata, Y.; Lei, Xuegong; Li, Yongjun; Turro, N. J.

    2015-03-01

    Water is the second molecule after hydrogen what has been trapped inside the cage of a C60 molecule by the molucular surgery method. We studied isolated water molecule isotopologs H2O, D2O, and HDO in the solid phase at cryogenic temperatures using IR spectroscopy. The water molecule rotation transitions were observed in the THz and vibration-rotation transitions in the mid-IR range. The slow conversion between para and ortho water allowed us to record the time evolution of spectra and to separate ortho and para absorption lines of water. The similarity of the rotation spectrum of caged water to water in the gas phase indicates that water is free to rotate in the C60 cage even at temperature as low as 3 K. However, spectral lines show a splitting of about 0.5 meV what is not compatible with the icosahedral symmetry of C60. Different models (e.g. crystal field effects in solid C60, C60 cage distortions) will be discussed. This work was supported by institutional research funding IUT23-3 of the Estonian Ministry of Education and Research.

  5. Mercator maps of orientations of a C60 molecule in single-walled nanotubes with distinct radii

    SciTech Connect

    Michel, K.H.; Verberck, B.; Nikolaev, A.V.

    2005-09-27

    We study the confinement of a C60 molecule encapsulated in a cylindrical nanotube as a function of the tube radius. Drawing the Mercator maps of the potential, we find two distinct molecular orientations; for tubes with small radii, RT < or approx. 7 A, a fivefold axis of the molecule coincides with the tube long axis, for larger radii, RT > or approx. 8 A, a threefold axis of the molecule coincides with the tube long axis. These different orientations are caused by the relative importance of the repulsive and the attractive parts of the van der Waals potentials of the molecule with the tube wall for small and large tubes respectively. Experimental evidence is provided by the apparent splitting of Ag modes of the C60 molecule in resonant Raman scattering.

  6. Features of self-aggregation of C60 molecules in toluene prepared by different methods

    NASA Astrophysics Data System (ADS)

    Makhmanov, Urol; Ismailova, Oksana; Kokhkharov, Abdulmutallib; Zakhidov, Erkin; Bakhramov, Sagdilla

    2016-05-01

    Structural and dimensional features of C60 aggregates in toluene solution prepared in two different ways - equilibrium and strongly non-equilibrium - were studied by high-resolution transmission electron microscopy and atomic-force microscopy methods. It was found that in solutions prepared by the non-equilibrium method (stirring of solution of C60 by a mechanical rotator), large quasispherical aggregates (with a diameter of up to ∼ 380 ± 20 nm) of nanoporous structure with fractal size D ≈ 2.13 were synthesized. In the case of solutions C60, which were prepared by the equilibrium method (without the use of external mechanical influences on solution), the formation of densely packed monomolecular fullerene aggregates with a diameter of not more than 50 nm was observed.

  7. Room-temperature repositioning of individual C60 molecules at Cu steps: Operation of a molecular counting device

    NASA Astrophysics Data System (ADS)

    Cuberes, M. T.; Schlittler, R. R.; Gimzewski, J. K.

    1996-11-01

    C60 molecules absorbed on a monoatomic Cu step have been reversibly repositioned at room temperature with the tip of a scanning tunneling microscope by performing controlled displacements along the step direction. We demonstrate the feasibility of building an abacus on the nanometer scale using single molecules as ``counters,'' Cu monoatomic steps as ``rods'' that constrain the molecular motion to one dimension, and the scanning tunneling microscope as an ``actuator'' for counting operations.

  8. Diffusion and self-assembly of C60 molecules on monolayer graphyne sheets

    PubMed Central

    Ozmaian, Masoumeh; Fathizadeh, Arman; Jalalvand, Morteza; Ejtehadi, Mohammad Reza; Allaei, S. Mehdi Vaez

    2016-01-01

    The motion of a fullerene (C60) on 5 different types of graphyne is studied by all-atom molecular dynamics simulations and compared with former studies on the motion of C60 on graphene. The motion shows a diffusive behavior which consists of either a continuous motion or discrete movements between trapping sites depending on the type of the graphyne sheet. For graphyne-4 and graphyne-5, fullerenes could detach from the surface of the graphyne sheet at room temperature which was not reported for similar cases on graphene sheets. Collective motion of a group of fullerenes interacting with a graphyne studied and it is shown that fullerenes exhibit stable assemblies. Depending on the type of graphyne, these assemblies can have either single or double layers. The mobility of the assembled structures is also dependent on the type of the graphyne sheet. The observed properties of the motion suggests novel applications for the complexes of fullerene and monolayer graphynes. PMID:26912386

  9. Phase separation analysis of bulk heterojunctions in small-molecule organic solar cells using zinc-phthalocyanine and C60

    NASA Astrophysics Data System (ADS)

    Schünemann, Christoph; Wynands, David; Wilde, Lutz; Hein, Moritz Philipp; Pfützner, Steffen; Elschner, Chris; Eichhorn, Klaus-Jochen; Leo, Karl; Riede, Moritz

    2012-06-01

    To achieve efficient organic solar cells, donor and acceptor molecules are mixed in the photoactive layer to form a so-called bulk heterojunction. Due to molecular interactions, a certain degree of phase separation between donor and acceptor domains arises, which is necessary to achieve efficient charge extraction within the absorber layer. However, the mechanism that induces the phase separation is not fully understood and gaining detailed information about the molecular arrangement within these blend layers is quite challenging. We show that grazing incidence x-ray diffraction, combined with variable angle spectroscopic ellipsometry is a suitable way to investigate the molecular structure of blend layers in detail, consisting of a mixture of zinc-phthalocyanine (ZnPc) and C60. The degree of phase separation within the blend layer is influenced by substrate heating during the co-evaporation of ZnPc and C60 and by a variation of the mixing ratio. The effect of different blend layer morphologies on optical and electrical device performance is investigated by solar cell characterization and mobility measurements. We find that the molecular arrangement of C60 provides the essential driving force for efficient phase separation. Whereas spherical C60 molecules are able to form crystalline domains when deposited at elevated substrate temperatures, no ZnPc crystallites are observed, although the planar ZnPc molecules are not randomly oriented but standing upright within its domains. Comparing specular and grazing incidence x-ray diffraction, we find that only the latter method is able to detect nanocrystalline C60 in thin films due to its polycrystalline nature and small sized nanocrystallites. Solar cell measurements show an increase in fill factor and external quantum efficiency signal for blends with enhanced phase separation, induced by higher substrate temperatures. However, grazing incidence x-ray diffraction measurements reveal that ZnPc and C60 already form

  10. Chemistry and temperature-assisted dehydrogenation of C60H30 molecules on TiO2(110) surfaces.

    PubMed

    Sánchez-Sánchez, Carlos; Martínez, José Ignacio; Lanzilotto, Valeria; Biddau, Giulio; Gómez-Lor, Berta; Pérez, Rubén; Floreano, Luca; López, María Francisca; Martín-Gago, José Ángel

    2013-11-21

    The thermal induced on-surface chemistry of large polycyclic aromatic hydrocarbons (PAHs) deposited on dielectric substrates is very rich and complex. We evidence temperature-assisted (cyclo)dehydrogenation reactions for C60H30 molecules and the subsequent bottom-up formation of assembled nanostructures, such as nanodomes, on the TiO2(110) surface. To this aim we have deposited, under ultra-high vacuum, a submonolayer coverage of C60H30 and studied, by a combination of experimental techniques (STM, XPS and NEXAFS) and theoretical methods, the different chemical on-surface interaction stages induced by the increasing temperature. We show that room temperature adsorbed molecules exhibit a weak interaction and freely diffuse on the surface, as previously reported for other aromatics. Nevertheless, a slight annealing induces a transition from this (meta)stable configuration into chemisorbed molecules. This adsorbate-surface interaction deforms the C60H30 molecular structure and quenches surface diffusion. Higher annealing temperatures lead to partial dehydrogenation, in which the molecule loses some of the hydrogen atoms and LUMO levels spread in the gap inducing a net total energy gain. Further annealing, up to around 750 K, leads to complete dehydrogenation. At these temperatures the fully dehydrogenated molecules link between them in a bottom-up coupling, forming nanodomes or fullerene-like monodisperse species readily on the dielectric surface. This work opens the door to the use of on-surface chemistry to generate new bottom-up tailored structures directly on high-K dielectric surfaces. PMID:24071968

  11. Movement of Ng2 molecules confined in a C60 cage: An ab initio molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Khatua, Munmun; Pan, Sudip; Chattaraj, Pratim K.

    2014-08-01

    An ab initio molecular dynamics study on Ng2@C60 (Ng = Hesbnd Kr) systems is performed to analyze the movement of Ng2 molecules inside a C60 cage. Within 500 fs time window, the He2 undergoes precession encompassing translation, vibration and rotation readily whereas other Ng2 molecules show usual vibration but the degrees of translation and rotation decrease with an increase in size of the Ng atoms. Increase in interaction between the Ng centers and cage carbons and an increased distortion of cage in moving from He to Kr seem to be responsible for this. During the movement, the Ng2 units behave as single entity. To check the kinetic stability of these systems through ab initio molecular dynamics study since they are thermodynamically unstable. Frenking et al. [40] argued about the free precession of the Ng2 units inside the cage on the basis of the very small energy differences between differently oriented Ng2 units. We need to check whether these Ng2 units really precess inside the C60 cage at room temperature and if yes then by what extent, up to 500 fs time scale. To check whether these weakly interacting He2 and Ne2 systems can be termed as molecules we would like to analyze the Ngsbnd Ng bond distance values at different time steps. In order to check the applicability of maximum hardness principle and minimum electrophilicity principle during time evolution of these endohedrally trapped systems the variation of hardness and electrophilicity with time during simulation and their correlation with the change in energy of the systems are studied.

  12. Quick synthesis of highly aligned or randomly oriented nanofibrous structures composed of C60 molecules via self-assembly

    NASA Astrophysics Data System (ADS)

    Kurosu, Shunji; Fukuda, Takahiro; Maekawa, Toru

    2013-06-01

    Assemblies, which are composed of nanoparticles such as nanofibres, have been intensively studied in recent years. This has particularly been the case in the field of biomedicine, where the aim is to develop efficient methodologies for capturing and separating target biomolecules and cells and/or encouraging bio-chemical reactions, utilizing the extremely high surface area to volume ratio of assemblies. There is an urgent need for the development of a quick synthesis method of forming nanofibrous structures on the surface of biomedical microchips and devices for the investigation of the interactions between biomolecules/cells and the nanostructures. Here, we produce nanofibrous structures composed of C60 molecules, which are aligned in one direction or randomly oriented, by dissolving C60 molecules and sulphur in benzene and evaporating a droplet of the solution on a glass substrate under appropriate conditions. The synthesis time is as short as 30 s. Sulphur is extracted and nanofibres are crystallized by leaving them in supercritical carbon dioxide.

  13. Charge transfer excitations in water-soluble sulfonated zinc-phthalocyanine (ZnPcS) donor molecules coupled to C60

    NASA Astrophysics Data System (ADS)

    Zope, Rajendra; Basurto, Luis; Olguin, Marco; Baruah, Tunna

    2013-03-01

    We present a study of charge transfer (CT) excited states for a recently synthesized group of water-soluble sulfonated zinc-phthalocyanine (ZnPcS) donor molecules coupled to C60. The ZnPcS donors (ZnPcS2, ZnPcS3, and ZnPcS4) are promising materials for achieving solar cell device production with the photoactive area prepared from aqueous solution. Experimentally, decreasing the number of sulfonate substituent groups for ZnPc increased the photocurrent and lowered the open circuit voltage VOC. Measurements show that the VOC is largest for ZnPc-S4/C60 and lowest for ZnPc-S3/C60. The degree of sulfonation and the measured device VOC does not result in the expected pattern of values based on donor-acceptor HOMO/LUMO energy differences. Variations in film morphology may account for the unexpected pattern of VOC values. Our charge transfer excited state calculations show that the lowest CT excitation energy among the group of ZnPcS/C60 donor-acceptor pairs corresponds to the disulfonated ZnPc/C60 system. The largest CT excited state energies belong to the tetrasulfonated ZnPc/C60 complex. We also examine the effect of geometrical orientation on the CT energies for the ZnPcS donor-acceptor pairs.

  14. New Volleyballenes: Y20C60 and La20C60

    PubMed Central

    Wang, Jing; Liu, Ying

    2016-01-01

    Two new stable Volleyballenes, the Y20C60 and La20C60 molecular clusters, are proposed on the basis of first-principles density functional theory. In conjunction with recent findings for the scandium system, these findings establish Volleyballene M20C60 molecules as a general class of stable molecules within the fullerene family. Both Y20C60 and La20C60 molecules have Th point group symmetries and relatively large HOMO-LUMO gaps. PMID:27487765

  15. New Volleyballenes: Y20C60 and La20C60

    NASA Astrophysics Data System (ADS)

    Wang, Jing; Liu, Ying

    2016-08-01

    Two new stable Volleyballenes, the Y20C60 and La20C60 molecular clusters, are proposed on the basis of first-principles density functional theory. In conjunction with recent findings for the scandium system, these findings establish Volleyballene M20C60 molecules as a general class of stable molecules within the fullerene family. Both Y20C60 and La20C60 molecules have Th point group symmetries and relatively large HOMO-LUMO gaps.

  16. New Volleyballenes: Y20C60 and La20C60.

    PubMed

    Wang, Jing; Liu, Ying

    2016-01-01

    Two new stable Volleyballenes, the Y20C60 and La20C60 molecular clusters, are proposed on the basis of first-principles density functional theory. In conjunction with recent findings for the scandium system, these findings establish Volleyballene M20C60 molecules as a general class of stable molecules within the fullerene family. Both Y20C60 and La20C60 molecules have Th point group symmetries and relatively large HOMO-LUMO gaps. PMID:27487765

  17. Charge transport in C60-based dumbbell-type molecules: mechanically induced switching between two distinct conductance states.

    PubMed

    Moreno-García, Pavel; La Rosa, Andrea; Kolivoška, Viliam; Bermejo, Daniel; Hong, Wenjing; Yoshida, Koji; Baghernejad, Masoud; Filippone, Salvatore; Broekmann, Peter; Wandlowski, Thomas; Martín, Nazario

    2015-02-18

    Single molecule charge transport characteristics of buckminsterfullerene-capped symmetric fluorene-based dumbbell-type compound 1 were investigated by scanning tunneling microscopy break junction (STM-BJ), current sensing atomic force microscopy break junction (CS-AFM-BJ), and mechanically controlled break junction (MCBJ) techniques, under ambient conditions. We also show that compound 1 is able to form highly organized defect-free surface adlayers, allowing the molecules on the surface to be addressed specifically. Two distinct single molecule conductance states (called high G(H)(1) and low G(L)(1)) were observed, depending on the pressure exerted by the probe on the junction, thus allowing molecule 1 to function as a mechanically driven molecular switch. These two distinct conductance states were attributed to the electron tunneling through the buckminsterfullerene anchoring group and fully extended molecule 1, respectively. The assignment of conductance features to these configurations was further confirmed by control experiments with asymmetrically designed buckminsterfullerene derivative 2 as well as pristine buckminsterfullerene 3, both lacking the G(L) feature. PMID:25651069

  18. Buckling of C60 whiskers

    NASA Astrophysics Data System (ADS)

    Asaka, Koji; Kato, Ryoei; Miyazawa, Kun'ichi; Kizuka, Tokushi

    2006-08-01

    The authors demonstrated the mechanics of materials for crystalline whiskers composed of C60 molecules; compressive deformation of the whiskers was observed by in situ transmission electron microscopy with simultaneous force measurement by means of an optical cantilever method, as used in atomic force microscopy. In response to compression along the long axis, the whiskers bent first elastically, then buckled. A whisker with 160nm diameter fractured brittlely at a strain of 0.08. According to Euler's formula, Young's modulus of the whisker was estimated to be 32-54GPa, which is 160%-650% of that of C60 bulk crystals.

  19. The encapsulated lithium effect on the first hyperpolarizability of C60Cl2 and C60F2.

    PubMed

    Song, Yao-Dong; Wang, Liang; Wu, Li-Ming; Chen, Qiao-Ling; Liu, Fa-Kun; Tang, Xiao-Wen

    2016-02-01

    In this paper, we report a study on the structure and first hyperpolarizability of C60Cl2 and C60F2. The calculation results show that the first hyperpolarizabilities of C60Cl2 and C60F2 were 172 au and 249 au, respectively. Compared with the fullerenes, the first hyperpolarizability of C60Cl2 increased from 0 au to 172 au, while the first hyperpolarizability of C60F2 increased from 0 au to 249 au. In order to further increase the first hyperpolarizability of C60Cl2 and C60F2, Li@C60Cl2 and Li@C60F2 were obtained by introducing a lithium atom to C60Cl2 and C60F2. The first hyperpolarizabilities of Li@C60Cl2 and Li@C60F2 were 2589 au and 985 au, representing a 15-fold and 3.9-fold increase, respectively, over those of C60Cl2 and C60F2. The transition energies of four molecules (C60Cl2, Li@C60Cl2, C60F2, Li@C60F2) were calculated, and were found to be 0.17866 au, 0.05229 au, 0.18385 au, and 0.05212 au, respectively. A two-level model explains why the first hyperpolarizability increases for Li@C60Cl2 and Li@C60F2. PMID:26841975

  20. C60 fullerene binding to DNA

    NASA Astrophysics Data System (ADS)

    Alshehri, Mansoor H.; Cox, Barry J.; Hill, James M.

    2014-09-01

    Fullerenes have attracted considerable attention in various areas of science and technology. Owing to their exceptional physical, chemical, and biological properties, they have many applications, particularly in cosmetic and medical products. Using the Lennard-Jones 6-12 potential function and the continuum approximation, which assumes that intermolecular interactions can be approximated by average atomic surface densities, we determine the binding energies of a C60 fullerene with respect to both single-strand and double-strand DNA molecules. We assume that all configurations are in a vacuum and that the C60 fullerene is initially at rest. Double integrals are performed to determine the interaction energy of the system. We find that the C60 fullerene binds to the double-strand DNA molecule, at either the major or minor grooves, with binding energies of -4.7 eV or -2.3 eV, respectively, and that the C60 molecule binds to the single-strand DNA molecule with a binding energy of -1.6 eV. Our results suggest that the C60 molecule is most likely to be linked to the major groove of the dsDNA molecule.

  1. Electronic structure, conductivity and superconductivity of metal doped C60

    SciTech Connect

    Haddon, R.C.

    1993-12-31

    The curvature and topology required for fullerene formation strongly enhances the electronegativity of the carbon clusters and as a result C60 readily accepts electrons. Solid C60 undergoes doping with a variety of metals to produce intercalation compounds which are conductors. In the case of the alkali metals the predominant phases present are: C60, A3C60, and A6C60. The A3C60 compounds are formed from C60 by occupancy of the interstitial sites of the fcc lattice. These phases constitute the first 3-dimensional organic conductors and for A=K, Rb the A3C60 compounds are superconductors with transition temperatures of Tc=19 and 28K, respectively. There is evidence to suggest that the superconductivity in these systems is driven by the intramolecular vibrations of the reduced C60 molecule. Recent experiments on a variety of metal doped C60 thin films will be presented.

  2. Sublimed C60 films for tribology

    NASA Astrophysics Data System (ADS)

    Bhushan, Bharat; Gupta, B. K.; Van Cleef, Garrett W.; Capp, Cindy; Coe, James V.

    1993-06-01

    Fullerenes take the form of hollow, geodesic domes, which are formed from a network of pentagons and hexagons. The C60 molecule has the highest possible symmetry (icosahedral) and assumes the shape of a soccer ball. At room temperature, fullerene molecules pack in a face-centered-cubic lattice bonded with weak van der Waals attractions. Fullerenes can be dissolved in solvents such as toluene and benzene and easily sublimed. The resilience, high load bearing capacity, low surface energy, high chemical stability, and spherical shape of C60 molecules and weak intermolecular bonding offer great potential for various mechanical and tribological applications. Sublimed films of C60 have been produced and friction and wear performance of these films in various operating environments are the subject of this letter.

  3. Properties Of N@C60-Derived Peapods

    NASA Astrophysics Data System (ADS)

    Gembus, A.; Simon, F.; Jánossy, A.; Kuzmany, H.; Dinse, K.-P.

    2004-09-01

    Using pulsed EPR techniques, the basic spin relaxation properties of N@C60-based peapods were determined. In contrast to narrow line spectra typical for N@C60 in solid solution or in a C60 matrix, substantial line broadening is observed for the SWCNT-encapsulated N@C60 molecules, which might be indicative for uniaxial cage distortion by interaction with the nanotube.

  4. Fullerene (C60) films for solid lubrication

    SciTech Connect

    Bhushan, B.; Gupta, B.K.; Van Cleef, G.W.; Capp, C.E.; Coe, J.V. )

    1993-10-01

    The advent of techniques for producing gram quantities of a new form of stable, pure, solid carbon, designated as fullerene, opens a profusion of possibilities to be explored in many disciplines including tribology. Fullerenes take the form of hollow geodesic domes, which are formed from a network of pentagons and hexagons with covalently bonded carbon atoms. The C60 molecule has the highest possible symmetry (icosahedral) and assumes the shape of a soccer ball. At room temperature, fullerene molecules pack in an fcc lattice bonded with weak van der Waals attractions. Fullerenes can be dissolved in solvents such as toluene and benzene and are easily sublimed. The low surface energy, high chemical stability, spherical shape, weak intermolecular bonding, and high load bearing capacity of C60 molecules offer potential for various mechanical and tribological applications. This paper describes the crystal structure and properties of fullerenes and proposes a mechanism for self-lubricating action. Sublimed films of C60 have been produced and friction and wear performance of these films in various operating environments are the subject of this paper. The results of this study indicate that C60, owing to its unique crystal structure and bonding, may be a promising solid lubricant. 31 refs.

  5. C_60 Nanotips for Scanning Tunneling Microscopy

    NASA Astrophysics Data System (ADS)

    Halas, N. J.

    1997-03-01

    Individual C_60 molecules are shown to provide stable conductive molecular tunneling sites, or nanotips, on the probe tip of a scanning tunneling microscope (STM). The chemisorptive attachment and subsequent imaging of discrete single molecules on an STM tip apex have been previously reported.(K. F. Kelly, D. Sarkar, S. Prato, J. S. Resh, G. D. Hale, and N. J. Halas, J. Vac. Sci. Tech. B14), 593 (1996). Functionalizing an STM tip with a C_60 molecular adsorbate alters the density of states near the Fermi energy of the tip tunneling site and modifies its imaging characteristics. These tips have permitted the observation of threefold symmetric electron scattering surrounding point defects on graphite surfaces, an effect which could not be observed using bare metal tips.(K. F. Kelly, D. Sarkar, G. D. Hale, S. J. Oldenburg, and N. J. Halas, Science 273), 1371 (1996).

  6. Superconductivity at 45 K in Rb/Tl codoped C60 and C60/C70 mixtures

    NASA Astrophysics Data System (ADS)

    Iqbal, Zafar; Baughman, Ray H.; Khare, Sandeep; Murthy, N. S.; Ramakrishna, B. L.; Bornemann, Hans J.; Morris, Donald E.

    1991-11-01

    The appearance of superconductivity at relatively high temperatures in alkali metal-doped C60 fullerene provides the challenge to both understand the nature and origin of the superconductivity and to determine the upper limit of the superconducting transition temperature (Tc). Toward the latter goal, it is shown that doping with potassium-thallium and rubidium-thallium alloys in the 400 to 430 C temperature range increases the Tc of C60/C70 mixtures to 25.6 K and above 45 K, respectively. Similar increases in Tc were also observed on analogous doping of pure C60. Partial substitution of potassium with thallium in interstitial sites between C60 molecules is suggested by larger observed unit cell parameters than for the K3C60 and K4C60 phases. Contrary to previous results for C60 doped with different alkali metals, such expansion does not alone account for the changes in critical temperature.

  7. Sc20C60: a volleyballene

    NASA Astrophysics Data System (ADS)

    Wang, Jing; Ma, Hong-Man; Liu, Ying

    2016-06-01

    An exceptionally stable hollow cage containing 20 scandium atoms and 60 carbon atoms has been identified. This Sc20C60 molecular cluster has a Th point group symmetry and a volleyball-like shape that we refer to below as ``Volleyballene''. Electronic structure analysis shows that the formation of delocalized π bonds between Sc atoms and the neighboring pentagonal rings made of carbon atoms is crucial for stabilizing the cage structure. A relatively large HOMO-LUMO gap (~1.4 eV) was found. The results of vibrational frequency analysis and molecular dynamics simulations both demonstrate that this Volleyballene molecule is exceptionally stable.An exceptionally stable hollow cage containing 20 scandium atoms and 60 carbon atoms has been identified. This Sc20C60 molecular cluster has a Th point group symmetry and a volleyball-like shape that we refer to below as ``Volleyballene''. Electronic structure analysis shows that the formation of delocalized π bonds between Sc atoms and the neighboring pentagonal rings made of carbon atoms is crucial for stabilizing the cage structure. A relatively large HOMO-LUMO gap (~1.4 eV) was found. The results of vibrational frequency analysis and molecular dynamics simulations both demonstrate that this Volleyballene molecule is exceptionally stable. Electronic supplementary information (ESI) available: Sc20C60: a Volleyballene_SI. See DOI: 10.1039/c5nr07784b

  8. Sc20C60: a volleyballene.

    PubMed

    Wang, Jing; Ma, Hong-Man; Liu, Ying

    2016-06-01

    An exceptionally stable hollow cage containing 20 scandium atoms and 60 carbon atoms has been identified. This Sc20C60 molecular cluster has a Th point group symmetry and a volleyball-like shape that we refer to below as "Volleyballene". Electronic structure analysis shows that the formation of delocalized π bonds between Sc atoms and the neighboring pentagonal rings made of carbon atoms is crucial for stabilizing the cage structure. A relatively large HOMO-LUMO gap (∼1.4 eV) was found. The results of vibrational frequency analysis and molecular dynamics simulations both demonstrate that this Volleyballene molecule is exceptionally stable. PMID:26878201

  9. Optimal High-TC Superconductivity in Cs3C60

    NASA Astrophysics Data System (ADS)

    Harshman, Dale; Fiory, Anthony

    The highest superconducting transition temperatures in the (A1-xBx)3C60 superconducting family are seen in the A15 and FCC structural phases of Cs3C60 (optimized under hydrostatic pressure), exhibiting measured values for near-stoichiometric samples of TC0 meas . = 37.8 K and 35.7 K, respectively. It is argued these two Cs-intercalated C60 compounds represent the optimal materials of their respective structures, with superconductivity originating from Coulombic e- h interactions between the C60 molecules, which host the n-type superconductivity, and mediating holes associated with the Cs cations. A variation of the interlayer Coulombic pairing model [Harshman and Fiory, J. Supercond. Nov. Magn. 28 ̲, 2967 (2015), and references therein] is introduced in which TC0 calc . ~ 1 / lζ , where l relates to the mean spacing between interacting charges on surfaces of the C60 molecules, and ζ is the average radial distance between the surface of the C60 molecules and the neighboring Cs cations. For stoichiometric Cs3C60, TC0 calc . = 38.08 K and 35.67 K for the A15 and FCC macrostructures, respectively; the dichotomy is attributable to differences in ζ.

  10. Energetics and structural characterization of C60 polymerization in BN and carbon nanopeapods

    NASA Astrophysics Data System (ADS)

    Trave, Andrea; Ribeiro, Filipe J.; Louie, Steven G.; Cohen, Marvin L.

    2004-11-01

    As in the case of carbon nanotubes, also boron nitride nanotubes may host arrays of C60 molecules and form a nanopeapod (NPP). The observed separation between C60 molecules in BN NPP’s is consistently shorter than in carbon NPP’s, which influences their electronic properties. Here we report on total-energy pseudopotential density functional theory (DFT) calculations for polymerized and nonpolymerized C60 chains, and optimize their atomic structures to provide a description of their energetic landscape. A fully polymerized C60 chain and a C60 dimer are found to be more stable than nonpolymerized C60 , respectively, by 0.89 and 0.38eV/C60 . The geometry and energetics of an encapsulated C60 chain is not significantly different with respect to the isolated molecule. Encapsulation energies in BN and carbon NPP’s are, respectively, 1.56 and 1.67eV/C60 , which are significantly larger than the calculated activation energy for C60 polymerization, supporting the hypothesis that encapsulated C60 ’s in NPP’s are partially polymerized. Band structure analysis show that polymerization does not affect the gap width of the C60 chain. BN NPP’s are semiconductors with a gap width determined by the C60 . The lowest unoccupied C60 states lie just above the Fermi level in metallic carbon NPP’s and charge transfert could take place, affecting the C60 geometry.

  11. Formation of buckminsterfullerene (C60) in interstellar space

    PubMed Central

    Berné, Olivier; Tielens, A. G. G. M.

    2012-01-01

    Buckminsterfullerene (C60) was recently confirmed as the largest molecule identified in space. However, it remains unclear how and where this molecule is formed. It is generally believed that C60 is formed from the buildup of small carbonaceous compounds in the hot and dense envelopes of evolved stars. Analyzing infrared observations, obtained by Spitzer and Herschel, we found that C60 is efficiently formed in the tenuous and cold environment of an interstellar cloud illuminated by strong ultraviolet (UV) radiation fields. This implies that another formation pathway, efficient at low densities, must exist. Based on recent laboratory and theoretical studies, we argue that polycyclic aromatic hydrocarbons are converted into graphene, and subsequently C60, under UV irradiation from massive stars. This shows that alternative—top-down—routes are key to understanding the organic inventory in space. PMID:22198841

  12. Formation of buckminsterfullerene (C60) in interstellar space

    NASA Astrophysics Data System (ADS)

    Berné, Olivier; Tielens, Alexander G. G. M.

    2012-01-01

    Buckminsterfullerene (C60) was recently confirmed to be the largest molecule identified in space. However, it remains unclear how, and where this molecule is formed. It is generally believed that C60 is formed from the build up of small carbonaceous compounds, in the hot and dense envelopes of evolved stars. Analyzing infrared observations, obtained by Spitzer and Herschel, we found that C60 is efficiently formed in the tenuous and cold environment of an interstellar cloud illuminated by strong ultraviolet (UV) radiation fields. This implies that another formation pathway, efficient at low densities, must exist. Based on recent laboratory and theoretical studies, we argue that Polycyclic Aromatic Hydrocarbons are converted into graphene, and subsequently C60, under UV irradiation from massive stars. This shows that alternative - top-down - routes are key to understanding the organic inventory in space.

  13. Orientation-dependent C-60 electronic structures revealed byphotoemission spectroscopy

    SciTech Connect

    Brouet, V.; Yang, W.L.; Zhou, X.J.; Choi, H.J.; Louie, S.G.; Cohen, M.L.; Goldoni, A.; Parmigiani, F.; Hussain, Z.; Shen, Z.X.

    2008-01-17

    We observe, with angle-resolved photoemission, a dramaticchange in the electronic structure of two C60 monolayers, deposited,respectively, on Ag (111) and (100) substrates, and similarly doped withpotassium to half filling of the C60 lowest unoccupied molecular orbital.The Fermi surface symmetry, the bandwidth, and the curvature of thedispersion at gamma point are different. Orient ations of the C60molecules on the two substrates are known to be the main structuraldifference between the two monolayers, and we present new band-structurecalculations for some of these orientations. We conclude thatorientations play a key role in the electronic structure offullerides.

  14. Evidence for endohedral muonium in K(x) C60 and consequences for electronic structure

    NASA Technical Reports Server (NTRS)

    Kiefl, R. F.; Duty, T. L.; Schneider, J. W.; Macfarlane, A.; Chow, K.; Elzey, J. W.; Mendels, P.; Morris, G. D.; Brewer, J. H.; Ansaldo, E. J.

    1992-01-01

    Positive muons injected into solid C60, K4C60, and K6C60 form vacuumlike muonium with a (6-12) percent probability. Observation of coherent spin precession of muonium establishes that all three materials are nonmagnetic and nonconducting at low temperatures. From the temperature dependence of the signals we estimate the electronic band gaps in K4C60 and K6C60 to be considerably smaller than in C60. The similarity of the muonium centers supports a model in which a muonium atom is caged inside the C60 molecule in pure C60 or the C60 exp -x molecular ion in K(x)C60.

  15. Superconductivity at 52 K in hole-doped C60.

    PubMed

    Schön, J H; Kloc, C; Batlogg, B

    2000-11-30

    Superconductivity in electron-doped C60 was first observed almost ten years ago. The metallic state and superconductivity result from the transfer of electrons from alkaline or alkaline-earth ions to the C60 molecule, which is known to be a strong electron acceptor. For this reason, it is very difficult to remove electrons from C60--yet one might expect to see superconductivity at higher temperatures in hole-doped than in electron-doped C60, because of the higher density of electronic states in the valence band than in the conduction band. We have used the technique of gate-induced doping in a field-effect transistor configuration to introduce significant densities of holes into C60. We observe superconductivity over an extended range of hole density, with a smoothly varying transition temperature Tc that peaks at 52 K. By comparison with the well established dependence of Tc on the lattice parameter in electron-doped C60, we anticipate that Tc values significantly in excess of 100 K should be achievable in a suitably expanded, hole-doped C60 lattice. PMID:11117735

  16. Intermolecular artifacts in probe microscope images of C60 assemblies

    NASA Astrophysics Data System (ADS)

    Jarvis, Samuel Paul; Rashid, Mohammad Abdur; Sweetman, Adam; Leaf, Jeremy; Taylor, Simon; Moriarty, Philip; Dunn, Janette

    2015-12-01

    Claims that dynamic force microscopy has the capability to resolve intermolecular bonds in real space continue to be vigorously debated. To date, studies have been restricted to planar molecular assemblies with small separations between neighboring molecules. Here we report the observation of intermolecular artifacts over much larger distances in 2D assemblies of C60 molecules, with compelling evidence that in our case the tip apex is terminated by a C60 molecule (rather than the CO termination typically exploited in ultrahigh resolution force microscopy). The complete absence of directional interactions such as hydrogen or halogen bonding, the nonplanar structure of C60, and the fullerene termination of the tip apex in our case highlight that intermolecular artifacts are ubiquitous in dynamic force microscopy.

  17. New Phases of C60 Synthesized at High Pressure

    NASA Astrophysics Data System (ADS)

    Iwasa, Y.; Arima, T.; Fleming, R. M.; Siegrist, T.; Zhou, O.; Haddon, R. C.; Rothberg, L. J.; Lyons, K. B.; Carter, H. L., Jr.; Hebard, A. F.; Tycko, R.; Dabbagh, G.; Krajewski, J. J.; Thomas, G. A.; Yagi, T.

    1994-06-01

    The fullerene C60 can be converted into two different structures by high pressure and temperature. They are metastable and revert to pristine C60 on reheating to 300^circC at ambient pressure. For synthesis temperatures between 300^circ and 400^circC and pressures of 5 gigapascals, a nominal face-centered-cubic structure is produced with a lattice parameter a_o = 13.6 angstroms. When treated at 500^circ to 800^circC at the same pressure, C60 transforms into a rhombohedral structure with hexagonal lattice parameters of a_o = 9.22 angstroms and c_o = 24.6 angstroms. The intermolecular distance is small enough that a chemical bond can form, in accord with the reduced solubility of the pressure-induced phases. Infrared, Raman, and nuclear magnetic resonance studies show a drastic reduction of icosahedral symmetry, as might occur if the C60 molecules are linked.

  18. C60 as a Probe for Astrophysical Environments

    NASA Astrophysics Data System (ADS)

    Brieva, A. C.; Gredel, R.; Jäger, C.; Huisken, F.; Henning, T.

    2016-08-01

    The C60 molecule has been recently detected in a wide range of astrophysical environments through its four active intramolecular vibrational modes (T 1u) near 18.9, 17.4, 8.5, and 7.0 μm. The strengths of the mid-infrared emission bands have been used to infer astrophysical conditions in the fullerene-rich regions. Widely varying values of the relative intrinsic strengths (RIS) of these four bands are reported in laboratory and theoretical papers, which impedes the derivation of the excitation mechanism of C60 in the astrophysical sources. The spectroscopic analysis of the C60 samples produced with our method delivers highly reproducible RIS values of 100, 25 ± 1, 26 ± 1 and 40 ± 4. A comparison of the inferred C60 emission band strengths with the astrophysical data shows that the observed strengths cannot be explained in terms of fluorescent or thermal emission alone. The large range in the observed 17.4 μm/18.9 μm emission ratios indicates that either the emission bands contain significant contributions from emitters other than C60, or that the population distribution among the C60 vibrational modes is affected by physical processes other than thermal or UV excitation, such as chemo-luminescence from nascent C60 or possibly Poincaré fluorescence resulting from an inverse internal energy conversion. We have carefully analyzed the effect of the weakly active fundamental modes and second order modes in the mid-infrared spectrum of C60, and propose that neutral C60 is the carrier of the unidentified emission band at 6.49 μm which has been observed in fullerene-rich environments.

  19. Assessment Of C60 As A Propellant Material For Ion Thrusters

    NASA Technical Reports Server (NTRS)

    Rapp, Don; Leifer, Stephanie D.

    1995-01-01

    Report presents analyses and data to support proposed use of C60 (buckminsterfullerene) as alternative to Xe, current propellent material of choice for use in ion thrusters. Concept of using C60 for this purpose described in "Electrostatic Propulsion Using C60 Molecules" (NPO-18526).

  20. Biological applications of hydrophilic C60 derivatives (hC60s)- a structural perspective.

    PubMed

    Zhu, Xiaolei; Sollogoub, Matthieu; Zhang, Yongmin

    2016-06-10

    Reactive oxygen species (ROS) generation and radical scavenging are dual properties of hydrophilic C60 derivatives (hC60s). hC60s eliminate radicals in dark, while they produce reactive oxygen species (ROS) in the presence of irradiation and oxygen. Compared to the pristine C60 suspension, the aqueous solution of hC60s is easier to handle in vivo. hC60s are diverse and could be placed into two general categories: covalently modified C60 derivatives and pristine C60 solubilized non-covalently by macromolecules. In order to present in detail, the above categories are broken down into 8 parts: C60(OH)n, C60 with carboxylic acid, C60 with quaternary ammonium salts, C60 with peptide, C60 containing sugar, C60 modified covalently or non-covalently solubilized by cyclodextrins (CDs), pristine C60 delivered by liposomes, functionalized C60-polymer and pristine C60 solubilized by polymer. Each hC60 shows the propensity to be ROS producer or radical scavenger. This preference is dependent on hC60s structures. For example, major application of C60(OH)n is radical scavenger, while pristine C60/γ-CD complex usually serves as ROS producer. In addition, the electron acceptability and innate hydrophobic surface confer hC60s with O2 uptake inhibition, HIV inhibition and membrane permeability. In this review, we summarize the preparation methods and biological applications of hC60s according to the structures. PMID:27049677

  1. Photocorrosion inhibition and enhancement of photocatalytic activity for ZnO via hybridization with C60.

    PubMed

    Fu, Hongbo; Xu, Tongguang; Zhu, Shengbao; Zhu, Yongfa

    2008-11-01

    C60 molecules with monomolecular layer state dispersed on the surface of ZnO and formed the hybridized interaction between ZnO and C60. C60-hybridized ZnO photocatalyst showed enhanced photocatalytic activity for the degradation of the organic dye and the photocorrosion of ZnO was successfully inhibited bythe hybridization of C60 molecules. The photocorrosion inhibition of ZnO by C60 molecule could be attributed to the reduced activation of surface oxygen atom. The enhanced photocatalytic activity for C60-hybridized ZnO was originated from the high migration efficiency of photoinduced electrons on the interface of C60 and ZnO, which was produced by the interaction of C60 and ZnO with a conjugative pi-system. The enhancement degree of photocatalytic activity was strongly depended on the coverage of C60 molecules on the surface of ZnO nanoparticles, and the optimum hybridization effect was found at a weight ratio of 1.5% (C60/ZnO). The hybridization of C60 with semiconductors could be used to improve the photocatalytic activity as well as the photostability. PMID:19031903

  2. Nanosegregation in Na2C60

    SciTech Connect

    Klupp, G.; Kamaras, K.; Matus, P.; Kiss, L.F.; Kovats, E.; Pekker, S.; Nemes, N.M.; Quintavalle, D.; Janossy, A.

    2005-09-27

    There is continuous interest in the nature of alkali metal fullerides containing C{sub 60}{sup 4-} and C{sub 60}{sup 2-}, because these compounds are believed to be nonmagnetic Mott-Jahn-Teller insulators. This idea could be verified in the case of A4C60, but Na2C60 is more controversial. By comparing the results of infrared spectroscopy and X-ray diffraction, we found that Na2C60 is segregated into 3-10 nm large regions. The two main phases of the material are insulating C60 and metallic Na3C60. We found by neutron scattering that the diffusion of sodium ions becomes faster on heating. Above 470 K Na2C60 is homogeneous and we show IR spectroscopic evidence of a Jahn-Teller distorted C{sub 60}{sup 2-} anion.

  3. Superconductivity in alkali-doped C60

    NASA Astrophysics Data System (ADS)

    Ramirez, Arthur P.

    2015-07-01

    Superconductivity in alkali-doped C60 (A3C60, A = an alkali atom) is well described by an s-wave state produced by phonon mediated pairing. Moderate coupling of electrons to high-frequency shape-changing intra-molecular vibrational modes produces transition temperatures (Tc) up to 33 K in single-phase material. The good understanding of pairing in A3C60 offers a paradigm for the development of new superconducting materials.

  4. Structural and Electrical Investigation of C60-Graphene Vertical Heterostructures.

    PubMed

    Kim, Kwanpyo; Lee, Tae Hoon; Santos, Elton J G; Jo, Pil Sung; Salleo, Alberto; Nishi, Yoshio; Bao, Zhenan

    2015-06-23

    Graphene, with its unique electronic and structural qualities, has become an important playground for studying adsorption and assembly of various materials including organic molecules. Moreover, organic/graphene vertical structures assembled by van der Waals interaction have potential for multifunctional device applications. Here, we investigate structural and electrical properties of vertical heterostructures composed of C60 thin film on graphene. The assembled film structure of C60 on graphene is investigated using transmission electron microscopy, which reveals a uniform morphology of C60 film on graphene with a grain size as large as 500 nm. The strong epitaxial relations between C60 crystal and graphene lattice directions are found, and van der Waals ab initio calculations support the observed phenomena. Moreover, using C60-graphene heterostructures, we fabricate vertical graphene transistors incorporating n-type organic semiconducting materials with an on/off ratio above 3 × 10(3). Our work demonstrates that graphene can serve as an excellent substrate for assembly of molecules, and attained organic/graphene heterostructures have great potential for electronics applications. PMID:26027690

  5. Photoemission study of Li@C60

    NASA Astrophysics Data System (ADS)

    Yagi, Hajime; Ogasawara, Naoko; Zenki, Masashi; Miyazaki, Takafumi; Hino, Shojun

    2016-05-01

    Ultraviolet and X-ray photoelectron spectra (UPS and XPS) of thin films prepared by either depositing or applying [Li@C60]+(PF6)- on the substrates are presented. The UPS and XPS of [Li@C60]+(PF6)- applied films suggest that PF6- anions come out from the surface by annealing at 250 °C. The UPS and XPS of the deposited thin films indicate that the film does not contain PF6- anion but is composed of only Li@C60. Changing the sublimation temperature reveals that encapsulated Li cations begin to escape from the C60 cage when heated above 550 °C.

  6. Theoretical study of the structures and first hyperpolarizabilities of C60Cl n and Li@C60Cl n (n = 4, 6, 8, 10).

    PubMed

    Song, Yao-Dong; Wang, Liang; Wu, Li-Ming

    2016-06-01

    We recently reported (Song Y-D et al., 2016, J Mol Model 22:50) that doping with Li greatly affects the static first hyperpolarizability of C60Cl2. In this work, with a view to creating nonlinear optical materials with high thermodynamic stability and wide transparent regions, a series of Li@C60Cl n (n = 4, 6, 8, 10) were designed. The structures, electrostatic potentials, electronic structures, absorption spectra, and linear and nonlinear optical properties of C60Cl n and Li@C60Cl n were systematically investigated using density functional theory (DFT) methods. The results of our calculations indicated that the stability of these molecules decreases in the order Li@C60Cl10 > Li@C60Cl8 > Li@C60Cl6 > Li@C60Cl4. It is clear that the number of Cl atoms greatly influences the stability of Li@C60Cl n . Li@C60Cl n showed greater thermodynamic stability than Li@C60Cl2. We also investigated the first hyperpolarizabilities of Li@C60Cl n and found them to be 2973, 3640, 4307, and 2627 au for n = 4, 6, 8, and 10, respectively-higher than that of Li@C60Cl2. Finally, we noted that the transparent region could be modulated by increasing the number of Cl atoms: Li@C60Cl n possess wider transparent regions than that of Li@C60Cl2. We therefore believe that this study has highlighted an effective method for designing nonlinear optical materials with high thermodynamic stability and wide transparent regions. PMID:27188724

  7. Protective Fullerene (C60) Packaging System for Microelectromechanical Systems Applications

    NASA Technical Reports Server (NTRS)

    Olivas, John D. (Inventor)

    2001-01-01

    The invention involves a method for locating the probe of a scanning tunneling micrograph a predetermined distance from its conducting surface, and specifically the deposition of a monolayer of fullerene C60 onto the conducting plate. The Fullerene C60 molecule is approximately spherical and a monolayer of fullerene has a thickness of one nanometer. By providing a monolayer of fullerene on the conducting surface and locating the probe on the surface of the monolayer, a distance of one nanometer can be established between the probe tip and the conducting surface.

  8. Quenching of fluorescence in C60 fulleropyrrolidines by chloroform

    NASA Astrophysics Data System (ADS)

    Parveen, Abdulrazack; Sughanya, Venkatesan; Nagarajan, Samuthira

    2016-01-01

    Functionalized [C60] fullerene, fulleropyrrolidines were synthesized and their photophysical properties are studied. The absorption and emission patterns are altered in fulleropyrrolidines, when compared with C60. Fluorescence of the molecules is quenched by CHCl3 in toluene solution at room temperature. Effect of nature and length of side chains in fulleropyrrolidine on quenching is investigated. Results suggested that the fluorescence intensity increased with increase in carbon chain length and the Stern-Volmer plot intercept values are indirectly proportional to the number of the carbons.

  9. Interaction of C(60) fullerene with lipids.

    PubMed

    Cataldo, Franco

    2010-06-01

    Unsaturated lipids when exposed to air at room temperature undergo a slow autoxidation. When fullerene C(60) was dissolved in selected lipids (ethyl oleate, ethyl linoleate, linseed oil and castor oil) the spectrophotometric analysis shows that the oxidation is concentrated to C(60) which is converted to an epoxide C(60)O. Thus, fullerene C(60) displays antioxidant activity not only when dissolved in unsaturated lipids but also, more generally, when dissolved in unsaturated solvents subjected to autoxidation like, for example, in cyclohexene. The behaviour of C(60) in ethyl oleate has been compared with that of the known antioxidant TMPPD (N,N',N,N,'-tetramethyl-p-phenylenediamine) in ethyl oleate. The mechanism of the antioxidant action of C(60) in lipids has been proposed. The kinetics of C(60) oxidation in lipids was determined spectrophotometrically both at room temperature in the dark and under UV irradiation. The oxidized products derived from C(60) photo-oxidation in lipids have been identified. PMID:20338159

  10. Nonlinear spectroscopy of C60 single crystal

    NASA Astrophysics Data System (ADS)

    Zamboni, Roberto; Muccini, Michele; Danieli, R.; Taliani, Carlo; Mohn, H.; Muller, W.; ter Meer, Hans-Ulrich

    1994-11-01

    Two-photon excitation measurements of C60 single crystal at 4 K have been performed. The TPE spectrum shows a sharp band at 1.846 eV which is assigned to the C60 lowest forbidden Frenkel singlet exciton of T1g symmetry. This assignment is supported by the analysis of Herzberg-Teller induced photoluminescence.

  11. 15 CFR 8c.60 - Communications.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 15 Commerce and Foreign Trade 1 2010-01-01 2010-01-01 false Communications. 8c.60 Section 8c.60 Commerce and Foreign Trade Office of the Secretary of Commerce ENFORCEMENT OF NONDISCRIMINATION ON THE... Communications. (a) The agency shall take appropriate steps to ensure effective communication with...

  12. 15 CFR 8c.60 - Communications.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 15 Commerce and Foreign Trade 1 2011-01-01 2011-01-01 false Communications. 8c.60 Section 8c.60 Commerce and Foreign Trade Office of the Secretary of Commerce ENFORCEMENT OF NONDISCRIMINATION ON THE... Communications. (a) The agency shall take appropriate steps to ensure effective communication with...

  13. 15 CFR 8c.60 - Communications.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 15 Commerce and Foreign Trade 1 2013-01-01 2013-01-01 false Communications. 8c.60 Section 8c.60 Commerce and Foreign Trade Office of the Secretary of Commerce ENFORCEMENT OF NONDISCRIMINATION ON THE... Communications. (a) The agency shall take appropriate steps to ensure effective communication with...

  14. Solubility of C60 in solvent mixtures.

    PubMed

    Kulkarni, Pradnya P; Jafvert, Chad T

    2008-02-01

    The potential large-scale production of fullerene C60 and its widespread use in consumer products may translate into occupational and public exposure and in long-term environmental exposure. To assess the risk and fate of C60 in the environment, it is important to understand its solvate formation in common industrial solvents as the solvates may affect various properties of C60 including reactivity and toxicity, particularly when solvates occur in C60 clusters. In this study, the solubility measurements in mixed solvent system can provide useful information about solvate formation. The solubility of C60 was measured in pure toluene, tetrahydrofuran, ethanol, and acetonitrile to be 3000, 11, 1.4, and 0.04 mg/L, respectively. Additionally, the solubility of C60 was measured in mixtures of toluene-acetonitrile, toluene-ethanol, toluene-tetrahydrofuran, and acetonitrile-tetrahydrofuran. The solubility data were modeled with some accuracy using Wohl's equation. The estimated crystal energy term for C60 in tetrahydrofuran was different than that in the other solvents, indicating that the C60 solid phase in equilibrium with tetrahydrofuran solution may be a solvated crystal. PMID:18323111

  15. Transport properties of the H2O@C60-dimer-based junction.

    PubMed

    Zhu, Chengbo; Wang, Xiaolin

    2015-09-23

    Theoretical predictions play an important role in finding potential applications in molecular electronics. Fullerenes have a number of potential applications, and the charge flow from a single C60 molecule to another becomes more versatile and more interesting after doping. Here, we report the conductance of two H2O@C60 molecules in series order and how the number of encapsulated water molecules influences the transport properties of the junction. Encapsulating an H2O molecule into one of the C60 cages increases the conductance of the dimer. Negative differential resistance is found in the dimer systems, and its peak-to-valley current ratio depends on the number of encapsulated H2O molecules. The conductance of the C60 dimer and the H2O@C60 dimer is two orders of magnitude smaller than that of the C60 monomer. Furthermore, we demonstrate that the conductance of the molecular junctions based on the H2O@C60 dimer can be tuned by moving the encapsulated H2O molecules. The conductance is H2O-position dependent. Our findings indicate that H2O@C60 can be used as a building block in C60-based molecular electronic devices and sensors. PMID:26325223

  16. Transport properties of the H2O@C60-dimer-based junction

    NASA Astrophysics Data System (ADS)

    Zhu, Chengbo; Wang, Xiaolin

    2015-09-01

    Theoretical predictions play an important role in finding potential applications in molecular electronics. Fullerenes have a number of potential applications, and the charge flow from a single C60 molecule to another becomes more versatile and more interesting after doping. Here, we report the conductance of two H2O@C60 molecules in series order and how the number of encapsulated water molecules influences the transport properties of the junction. Encapsulating an H2O molecule into one of the C60 cages increases the conductance of the dimer. Negative differential resistance is found in the dimer systems, and its peak-to-valley current ratio depends on the number of encapsulated H2O molecules. The conductance of the C60 dimer and the H2O@C60 dimer is two orders of magnitude smaller than that of the C60 monomer. Furthermore, we demonstrate that the conductance of the molecular junctions based on the H2O@C60 dimer can be tuned by moving the encapsulated H2O molecules. The conductance is H2O-position dependent. Our findings indicate that H2O@C60 can be used as a building block in C60-based molecular electronic devices and sensors.

  17. Mapping intermolecular bonding in C60

    PubMed Central

    Sundqvist, Bertil

    2014-01-01

    The formation of intermolecular bonds in C60 has been investigated in detail at pressures below 2.2 GPa and up to 750 K. Fullerene samples were heated in a temperature gradient to obtain data on the formation of dimers and low-dimensional polymers along isobars. Intermolecular bonding was analyzed ex situ by Raman scattering, using both intramolecular modes and intermolecular stretching modes. Semi-quantitative reaction maps are given for the formation of dimers and chains. The activation energy for dimer formation decreases by 0.2 meV pm−1 when intermolecular distances decrease and dimer formation is noticeably affected by the rotational state of molecules. Above 400–450 K larger oligomers are formed; below 1.4 GPa most of these are disordered, with small domains of linear chains, but above this the appearance of stretching modes indicates the existence of ordered one-dimensional polymers. At the highest pressures and temperatures two-dimensional polymers are also observed. PMID:25145952

  18. A study of thermally activated delayed fluorescence in C 60

    NASA Astrophysics Data System (ADS)

    Salazar, Filipa A.; Fedorov, Aleksandre; Berberan-Santos, Mário N.

    1997-06-01

    The existence of thermally activated delayed fluorescence in C 60 is demonstrated by the study of the temperature dependence (291-353 K) of the fluorescence intensity of C 60 degassed solutions. The determined singlet-triplet energy gap, 35 ± 2 kJ/mol, agrees with the value calculated from previously reported fluorescence and low temperature phosphorescence spectra for this molecule (35 kJ/mol). The estimated quantum yield of triplet formation, 0.8 ± 0.1, agrees with previous determinations. The fluorescence lifetime of C 60, also measured, τ = 1.1 ns, does not change appreciably with excitation wavelength, degassing nor with temperature, in the range 243-343 K.

  19. Electron transport properties and spin modulation effect analysis for C60, Au@C60 and Ag@C60

    NASA Astrophysics Data System (ADS)

    Wang, Fangyuan; Li, Guiqin

    2016-04-01

    The electron transport properties of C60, Au@C60 and Ag@C60 junctions between Au electrodes are investigated with density functional theory and the first-principle nonequilibrium Greens function. Density of states and transmission possibility as functions of energy are examined, and current-voltage characteristics of all these models are calculated with and without spin correction. With spin correction, we find a spin-current difference in Au@C60 as large as an order of magnitude. It may be used to obtain high-purity arbitrary spin current. By comparing the calculation results with and without spin correction, we attribute this spin difference to the spin resonance between transmission electrons and the valence electron of endohedral Au atom.

  20. Electronically Excited C2 from Laser Photodissociated C60

    NASA Technical Reports Server (NTRS)

    Arepalli, Sivaram; Scott, Carl D.; Nikolaev, Pavel; Smalley, Richard E.

    1999-01-01

    Spectral and transient emission measurements are made of radiation from products of laser excitation of buckminsterfullerene (C60) vapor diluted in argon at 973 K. The principal radiation is from the Swan band system of C2 and, at early times, also from a black body continuum. The C2 radiation is observed only when C60 is excited by green (532 nm) and not with IR (1064 nm) laser radiation at energy densities of about 1.5 J/square cm. Transient measurements indicate that there are two characteristic periods of decay of radiation. The first period, lasting about 2 micro seconds, has a characteristic decay time of about 0.3 micro seconds. The second period, lasting at least 50 micro seconds, has a characteristic decay time of about 5 micro seconds. These characteristic times are thought to be associated with cooling of C60 molecules or nanosized carbon particles during the early period; and with electronically excited C2 that is a decomposition product of laser excited C60, C58, ... molecules during the later period.

  1. Fluoride inhibition of inorganic pyrophosphatase. II. Isolation and characterization of a covalent intermediate between enzyme and entire substrate molecule.

    PubMed

    Baykov, A A; Bakuleva, N P; Nazarova, T I; Avaeva, S M

    1977-03-15

    A presumed pyrophosphoryl-enzyme intermediate of the reaction catalyzed by bakers' yeast inorganic pyrophosphatase pyrophosphate phosphohydrolase, EC 3.6.1.1) has been isolated using fluoride-mediated inactivation of the enzyme during catalysis. The analysis of the F--inactivated pyrophosphatase revealed the presence of one molecule of PPi and one atom of fluoride per active site. The incubation of the inactivated enzyme at 25 degrees C and pH 7.2 resulted in gradual recovery of catalytic activity and concomitant removal of PPi by a first-order reaction with tau1/2 of 1 h. The digestion of the F--treated pyrophosphatase with pepsin yielded phosphorous-containing peptides, which were reduced with NaBH4 and gave homoserine and homoserine lactone after acid hydrolysis. This suggests that the PPi residue is linked to the protein through a bond of an acyl phosphate type involving the beta-COOH function of aspartic acid. Together with the results of the kinetic studies of fluoride inhibition of pyrophosphatase reported in accompanying papers, these findings strongly indicate that the enzyme-substrate compound stabilized by fluoride is a transient of the catalytic reaction. PMID:843537

  2. First-principles investigation of organic photovoltaic materials C60, C70, [C60]PCBM , and bis-[C60]PCBM using a many-body G0W0 -Lanczos approach

    NASA Astrophysics Data System (ADS)

    Qian, Xiaofeng; Umari, Paolo; Marzari, Nicola

    2015-06-01

    We present a first-principles investigation of the excited-state properties of electron acceptors in organic photovoltaics including C60, C70, [6,6]-phenyl-C61-butyric-acid-methyl-ester ([C60]PCBM ), and bis-[C60]PCBM using many-body perturbation theory within the Hedin's G0W0 approximation and an efficient Lanczos approach. Calculated vertical ionization potentials (VIP) and vertical electron affinities (VEA) of C60 and C70 agree very well with experimental values measured in the gas phase. The density of states of all three molecules is also compared to photoemission and inverse photoemission spectra measured on thin films, and they exhibit a close agreement—a rigid energy-gap renormalization owing to intermolecular interactions in the thin films. In addition, it is shown that the low-lying unoccupied states of [C60]PCBM are all derived from the highest-occupied molecular orbitals and the lowest-unoccupied molecular orbitals of fullerene C60. The functional side group in [C60]PCBM introduces a slight electron transfer to the fullerene cage, resulting in small decreases of both VIP and VEA. This small change of VEA provides a solid justification for the increase of open-circuit voltage when replacing fullerene C60 with [C60]PCBM as the electron acceptor in bulk heterojunction polymer solar cells.

  3. Preparation of C60 by Detonation Technique

    NASA Astrophysics Data System (ADS)

    Wei, Xianfeng; Han, Yong; Long, Xinping

    2012-11-01

    A mixture of TNT (Trinitrotoluene) and natural graphite was detonated in a vacuum container which was immersed into cooling water; detonation products were collected for detecting. The results of mass spectroscopy, high performance liquid chromatography showed significant signals of C60, which proved that C60 could be synthesized by detonating the mixture of TNT/graphite and the detonation pressure was around 12.3 GPa and the detonation temperature was around 1985 K.

  4. Hugoniot of C60 fullerite: new results

    NASA Astrophysics Data System (ADS)

    Milyavskiy, Vladimir; Utkin, Alexander; Zhuk, Andrey; Yakushev, Vladislav; Fortov, Vladimir

    2005-07-01

    Recently, we have experimentally studied shock compressibility of C60 fullerite and sound velocity in shock-compressed fullerite at the pressure range up to ˜50 GPa [1]. In this work we present the results of new shock experiments executed with C60 fullerite in the same pressure range. On the base of new experimental results, we have made some correction of our concept [1] of the processes occurring in C60 fullerite at shock compression. In particular, the anomalous behavior of the rear surface velocity profiles was detected at pressure ˜9 GPa [1]. Additional experiments have shown that this anomalous behavior was caused by jump of the sound velocity in C60 because of formation of more hard carbon phase. We assume that it is a polymerized C60 phase. In the pressure region 9-25 GPa, destruction of this phase and formation of a graphite-like carbon occurs. With further growth of shock pressure, phase transition of the graphite-like carbon to a diamond-like phase is observed with a transition onset pressure ˜25 GPa. If shock pressures higher than ˜33 GPa, Hugoniot of C60 is determined by the thermodynamic properties of the diamond-like phase. [1] V.V. Milyavskiy, A.V. Utkin, E.B. Zaretsky, A.Z. Zhuk, V.V. Yakushev, V.E. Fortov. AIP CP 706 (2004) 667.

  5. IR absorptions of C60(+) and C60(-) in neon matrixes.

    PubMed

    Kern, Bastian; Strelnikov, Dmitry; Weis, Patrick; Böttcher, Artur; Kappes, Manfred M

    2013-08-29

    C60(+) ions were produced by electron-impact ionization of sublimed C60, collimated into an ion beam, turned 90° by an electrostatic deflector to separate them from neutrals, mass filtered by a radio frequency quadrupole, and co-deposited with Ne on a cold 5 K gold-coated sapphire substrate. Infrared absorption spectroscopy revealed the additional presence of C60 and C60(-) in the as-prepared cryogenic matrixes. To change the C60(+)/C60(-) ratio, CCl4 or CO2 electron scavengers were added to the matrix gas. Also taking into account DFT calculations, we have identified nine new previously unpublished IR absorptions of C60(+) and seven of C60(-) in Ne matrixes. Our measurements are in very good agreement with DFT calculations, predicting D5d C60(+) and D3d C60(-) ground states. The new results may be of interest regarding the presence of C60 and C70 (as well as ions thereof) in Space. PMID:23902528

  6. Yttrium-dispersed C60 fullerenes as high-capacity hydrogen storage medium

    NASA Astrophysics Data System (ADS)

    Tian, Zi-Ya; Dong, Shun-Le

    2014-02-01

    Interaction between hydrogen molecules and functionalized C60 is investigated using density functional theory method. Unlike transition metal atoms that tend to cluster on the surface, C60 decorated with 12 Yttrium atoms on each of its 12 pentagons is extremely stable and remarkably enhances the hydrogen adsorption capacity. Four H2 molecules can be chemisorbed on a single Y atom through well-known Dewar-Chatt-Duncanson interaction. The nature of bonding is a weak physisorption for the fifth adsorbed H2 molecule. Consequently, the C60Y12 complex with 60 hydrogen molecules has been demonstrated to lead to a hydrogen storage capacity of ˜6.30 wt. %.

  7. James C. McGroddy Prize Talk: What Was New About C60

    NASA Astrophysics Data System (ADS)

    Haddon, Robert

    2008-03-01

    C60 was named molecule of the year by Science in 1991, and in this talk I will discuss what I consider to be the most novel features of the molecule. In some ways C60 is truly unique and the discovery of the molecule in 1985 and its subsequent synthesis in 1990 blazed a trail of new chemical and physical properties that is unlikely to be surpassed by any other molecule. I will discuss the electronic structure of C60, its magnetism, and the conductivity and superconductivity shown by the alkali metal-doped phases.

  8. Nitrogen-embedded buckybowl and its assembly with C60

    PubMed Central

    Yokoi, Hiroki; Hiraoka, Yuya; Hiroto, Satoru; Sakamaki, Daisuke; Seki, Shu; Shinokubo, Hiroshi

    2015-01-01

    Curved π-conjugated molecules have attracted considerable interest because of the unique properties originating from their curved π surface. However, the synthesis of such distorted molecules requires harsh conditions, which hamper easy access to heteroatom-containing curved π systems. Here we report the synthesis of a π-extended azacorannulene with nitrogen in its centre. The oxidation of 9-aminophenanthrene provides tetrabenzocarbazole, which is converted to the azabuckybowl through palladium-catalysed intramolecular coupling. The electron-donating nature and curved π surface of the azabuckybowl enable its tight association with C60 in solution and solid states. High charge mobility is observed for the azabuckybowl/C60 assembly. This compound may be of interest in the fields of curved π systems as fullerene hosts, anisotropic π donors and precursors to nitrogen-containing nanocarbon materials. PMID:26337912

  9. C60 oxide as a key component of aqueous C60 colloidal suspensions.

    PubMed

    Murdianti, Befrika S; Damron, Joshua T; Hilburn, Martha E; Maples, Randall D; Hikkaduwa Koralege, Rangika S; Kuriyavar, Satish I; Ausman, Kevin D

    2012-07-17

    Stable aqueous fullerene colloidal suspensions (nC(60)) are demonstrated to rely on the [6,6]-closed epoxide derivative of the fullerene (C(60)O) for stability. This derivative is present, though often unrecognized, in small quantities in nearly all C(60) starting materials due to a reaction with air. The low-yield formation of nC(60) from organic solvent solutions results from a preferential partitioning and thus enrichment of C(60)O in the colloidal particles. This partitioning is significantly retarded in the nC(60) synthesis method that does not involve organic solvent solutions: long-term stirring in water. Instead, this method relies on trace levels of ozone in the ambient atmosphere to produce sufficient C(60)O at the surfaces of the nC(60) particles to allow stable suspension in water. Controlled-atmosphere syntheses, deliberate C(60)O enrichment, light scattering measurements, and extraction followed by HPLC analysis and UV-visible absorption spectroscopy support the above model of nC(60) formation and stabilization. PMID:22703564

  10. SiC formation on Si(100) via C 60 precursors

    NASA Astrophysics Data System (ADS)

    De Seta, M.; Tomozeiu, N.; Sanvitto, D.; Evangelisti, F.

    2000-07-01

    The interaction between C 60 molecules and the Si(100) surface and the preparation of silicon-carbide thin films by thermal reaction of C 60 molecules with the Si(100) surface have been investigated using X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, reflection high-energy electron diffraction and atomic force microscopy measurements. The effects of annealing temperature and C 60 coverage on the SiC formation will be discussed. It is found that the C 60 molecules bond covalently with silicon, and the number of bonds increase upon increasing the annealing temperature. Annealing at T≥830°C entails the formation of stoichiometric silicon carbide clusters that coalesce to form a continuous SiC layer when the C 60 coverage is greater than one monolayer. Deep pits acting as silicon diffusion channels are present with dimensions that increase with the amounts of C 60. The interaction of C 60 with the SiC surface was also investigated. It is found that a similar covalent interaction is present in the two systems C 60/Si and C 60/SiC.

  11. Protective Fullerene (C60) Packaging System for Microelectromechanical Systems Applications

    NASA Technical Reports Server (NTRS)

    Olivas, John D. (Inventor)

    2004-01-01

    The invention involves tunneling tips to their conducting surface, and specifically the deposition of a monolayer of fullerene C60 onto the conducting plate surface to protect the tunneling tip from contact. The Fullerene C60 molecule is approximately spherical, and a monolayer of fullerene has a thickness of one nanometer, such that a monolayer thereby establishing the theoretical distance desired between the MEMS tunneling tip and the conducting plate. Exploiting the electrical conductivity of C60 the tip can be accurately positioned by simply monitoring conductivity between the fullerene and the tunneling tip. By monitoring the Conductivity between the tip and the fullerene layer as the tip is brought in proximity, the surfaces can be brought together without risk of contacting the underlying conducting surface. Once the tunneling tip is positioned at the one nanometer spacing, with only the monolayer of fullerene between the tunneling tip and the conducting plate, the monolayer of C60, can be broken down thermally and removed chemically leaving only the tunneling tip and the conducting plate at the ideal tunneling spacing. Alternatively, the properties of fullerene allow the tunneling process to occur directly across the fullerene monolayer.

  12. Orientational and magnetic ordering of buckyballs in TDAE-C60

    SciTech Connect

    Mihailovic, D.; Arcon, D.; Venturini, P.; Blinc, R.; Omerzu, A.; Cevc, P.

    1995-04-01

    Spin ordering in the low-temperature magnetic phase is directly linked to the orientational ordering of C60 molecules in organically doped fullerene derivatives. Electron spin resonance and alternating current susceptometry measurements on tetrakis (dimethylamino) ethylene-C60 (TDAE-C60) (Curie temperature T(sub c) = 16 kelvin) show a direct coupling between spin and merohedral degrees of freedom. This coupling was experimentally demonstrated by showing that ordering the spins in the magnetic phase imprints a merohedral order on the solid or, conversely, that merohedrally ordering the C60 molecules influences the spin order at low temperature. The merohedral disorder gives rise to a distribution of pi-electron exchange interactions between spins on neighboring C60 molecules, suggesting a microscopic origin for the observed spin-glass behavior of the magnetic state. 18 refs.

  13. Inversion Symmetry Breaking in Endohedral C_60

    NASA Astrophysics Data System (ADS)

    Clougherty, Dennis; Anderson, Frederick

    1998-03-01

    A pseudo--Jahn--Teller model describing central atom distortions is proposed for endohedral fullerenes of the form A@C_60 where A is either a rare gas or a metal atom. A critical (dimensionless) coupling gc is found, at or below which the symmetric configuration is stable and above which inversion symmetry is broken. Vibronic parameters are given for selected endohedral fullerenes.

  14. Ortho-para conversion of endohedral water in the fullerene C60 at cryogenic temperatures

    NASA Astrophysics Data System (ADS)

    Shugai, Anna; Nagel, U.; Rõõm, T.; Mamone, S.; Concistrè, M.; Meier, B.; Krachmalnicoff, A.; Whitby, R. J.; Levitt, M. H.; Lei, Xuegong; Li, Yongjun; Turro, N. J.

    2015-03-01

    Water displays the phenomenon of spin isomerism in which the two proton spins either couple to form a triplet (ortho water, I = 1) or a singlet nuclear spin state (para water, I = 0). Here we study the interconversion of para and ortho water. The exact mechanism of this process is still not fully understood. In order to minimize interactions between molecules we use a sample where a single H2O is trapped in the C60 molecular cage (H2O@C60)andH2O@C60iscrystallized.H2O@C60 has long-lived ortho state and ortho-para conversion kinetics is non-exponential at LHeT. We studied mixtures of H2O@C60, D2O@C60 and C60 using IR absorption, NMR and dielectric measurements. We saw the speeding up of the interconversion with the growth of H2O@C60 concentration in C60 or when D2O@C60 was added. At some temperatures the kinetics is exponential. Models are discussed in order to explain the T and concentration dependence of ortho-para interconversion kinetics. This work was supported by institutional research funding IUT23-3 of the Estonian Ministry of Education and Research.

  15. Quantum Bound States in a C-C60 System

    NASA Astrophysics Data System (ADS)

    Adam, R. M.; Sofianos, S. A.

    2015-03-01

    We investigate the quantum mechanical system of a carbon "test atom" in the proximity of a C60 molecule, both inside and outside the fullerene "cage". Two sets of bound states are found to exist, a deeply bound set inside the cage and another weakly bound set outside it. Tunnelling between these regions is highly unlikely to happen because of the extreme height and width of the potential barrier. However, we predict that a layer of atoms could be adsorbed onto C60 by forming a quantum mechanical bound state, with the adsorbed atoms being concentrated above the "panels" of the buckyball, consistent with "bucky onions" observed experimentally. Until now analysis of such fullerene systems has been via classical mechanics, but a quantum approach reveals new insights.

  16. Synthesis of C60H2 by rhodium-catalyzed hydrogenation of C60

    NASA Technical Reports Server (NTRS)

    Becker, L.; Evans, T. P.; Bada, J. L.; Miller, S. L. (Principal Investigator)

    1993-01-01

    Reduction of C60 with rhodium(0) on alumina and hydrogen in deuterated benzene (C6D6) at ambient temperature and pressure yields a mixture of hydrogenated compounds; C60H2 has been characterized as the major product in 14% yield based on 1H NMR.

  17. Charge transfer and formation of conducting C60 monolayers at C60/noble-metal interfaces

    NASA Astrophysics Data System (ADS)

    Nouchi, Ryo; Kanno, Ikuo

    2005-05-01

    The resistance of a conducting C60 monolayer formed on a polycrystalline Ag film was found to be 0.7±0.1kΩ by in situ resistance measurements. By another series of in situ resistance measurements, the surface scattering cross sections, whose magnitude represents the relative amount of transferred charge, were evaluated as 100Å2 for C60/Au, and 150Å2 for C60/Cu and C60/Ag systems. However, comparison with previous results obtained for monolayers formed on Au and Cu films showed that the resistances of conducting C60 monolayers do not show a simple dependence on the transferred charge. Atomic force microscopy measurements revealed that the grain size of the underlying noble metals also plays an important role.

  18. Raman study on a bulk-heterojunction film of pentacene and C60

    NASA Astrophysics Data System (ADS)

    Iwasawa, Yasuhiro; Furukawa, Yukio

    2015-09-01

    We measured the 785-nm excited Raman spectrum of a pentacene:C60 blend film. The 1462-, 492-, and 268-cm-1 bands of C60 showed broadening in bandwidth and downward shifts in peak wavenumbers, whereas such broadening and downward shifts were not observed for pentacene. These results indicate that there are pentacene crystallites among the amorphous C60. The intensity ratio of the 1598-cm-1 (B3g) and the 1534-cm-1 (Ag) bands indicates that pentacene molecules have standing orientations. The appearance of a 514-cm-1 band (F1u) and the splitting of the Hg bands of C60 indicate symmetry lowering induced by the interaction between pentacene and C60 molecules.

  19. Blocking the passage: C60 geometrically clogs K(+) channels.

    PubMed

    Calvaresi, Matteo; Furini, Simone; Domene, Carmen; Bottoni, Andrea; Zerbetto, Francesco

    2015-05-26

    Classical molecular dynamics (MD) simulations combined with docking calculations, potential of mean force estimates with the umbrella sampling method, and molecular mechanic/Poisson-Boltzmann surface area (MM-PBSA) energy calculations reveal that C60 may block K(+) channels with two mechanisms: a low affinity blockage from the extracellular side, and an open-channel block from the intracellular side. The presence of a low affinity binding-site at the extracellular entrance of the channel is in agreement with the experimental results showing a fast and reversible block without use-dependence, from the extracellular compartment. Our simulation protocol suggests the existence of another binding site for C60 located in the channel cavity at the intracellular entrance of the selectivity filter. The escape barrier from this binding site is ∼21 kcal/mol making the corresponding kinetic rate of the order of minutes. The analysis of the change in solvent accessible surface area upon C60 binding shows that binding at this site is governed purely by shape complementarity, and that the molecular determinants of binding are conserved in the entire family of K(+) channels. The presence of this high-affinity binding site conserved among different K(+) channels may have serious implications for the toxicity of carbon nanomaterials. PMID:25873341

  20. On the vibrational modes of C 60

    NASA Astrophysics Data System (ADS)

    Clougherty, Dennis P.; Gorman, John P.

    1996-03-01

    The vibrational spectrum of C 60 is compared to the spectrum of a classical isotropic elastic spherical shell. We show correlations between the low frequency modes of C 60 and those of the spherical shell. We find the spherical model gives the approximate frequency ordering for the low frequency modes. We estimate a Poisson ratio of σ ≈ 0.30 and a transverse speed of sound of υs ≈ 1800 m/s for the equivalent elastic shell. We also find that ω( M1) /ω( M0) = √ 3/2 for the shell modes M 0 and M 1, independent of elastic constants. We find that this ratio compares favorably with an experimental value of 1.17.

  1. Ferroelectricity in (K@C60)n

    NASA Astrophysics Data System (ADS)

    Clougherty, Dennis P.

    2000-09-01

    A theoretical analysis of the ground state of long-chain (K@C60)n is presented. Within mean field theory, a ferroelectric ground state is found to be stable because of the pseudo-Jahn-Teller mixing of the b1u and the b2g band with a zone-center optical phonon involving the displacement of the endohedral K- ions. A phase diagram for this model is derived in the narrow bandwidth regime.

  2. Electronic pair binding and Hund's rule violations in doped C60

    NASA Astrophysics Data System (ADS)

    Jiang, Hong-Chen; Kivelson, Steven

    2016-04-01

    We calculate the electronic properties of the t -J model on a C60 molecule using the density-matrix renormalization group and show that Hund's first rule is violated and that for an average of three added electrons per molecule, an effective attraction (pair binding) arises for intermediate values of t /J . Specifically, it is energetically favorable to put four electrons on one C60 and two on a second rather than putting three on each. Our results show that a dominantly electronic mechanism of superconductivity is possible in doped C60.

  3. Electronic Structure of Crystalline Buckyballs: fcc-C60

    NASA Astrophysics Data System (ADS)

    Jalali-Asadabadi, Saeid; Ghasemikhah, E.; Ouahrani, T.; Nourozi, B.; Bayat-Bayatani, M.; Javanbakht, S.; Aliabad, H. A. Rahnamaye; Ahmad, Iftikhar; Nematollahi, J.; Yazdani-Kachoei, M.

    2016-01-01

    The electronic properties of pristine fcc-C60 are calculated by utilizing a variety of density functional theory (DFT) approaches including the Perdew-Burke-Ernzerhof generalized gradient approximation (PBE-GGA), PBE-GGA+DFT-D3(vdW), Engel and Vosko GGA (EV-GGA), GGA plus Hubbard U parameter (GGA+U), hybrids Becke-Perdew-Wang hybrid functional (B3PW91), Becke-Lee-Yang-Parr hybrid functional (B3LYP), the PBE exchange-correlation functional (PBE0), and Tran and Blaha regular and non-regular modified Becke and Johnson (TB-mBJ) potential within a DFT frame work using augmented plane waves plus local orbital method. The comparison of the calculated results with the experimental values shows that the non-regular TB-mBJ method reproduces a correct experimental direct band gap of 2.12 eV at X symmetry for this compound. The effectiveness of this theoretical approach in the reproduction of the experimental band gap is due to the proper treatment of the electrons in the interstitial region of the crystal. Our results show that the C60 clusters are weakly interacting with each other in the fcc crystal. This study also reveals that the five-fold degeneracies of the isolated C60 molecule due to its icosahedral symmetry are completely lifted at an X symmetry point by the crystal field.

  4. C60-derived nanobaskets: stability, vibrational signatures, and molecular trapping.

    PubMed

    dos Santos, S G; Pires, M S; Lemos, V; Freire, V N; Caetano, E W S; Galvão, D S; Sato, F; Albuquerque, E L

    2009-09-30

    C(60)-derived nanobaskets, with chemical formulae (symmetry point group) C(40)H(10) (C(5v)), C(39)H(12) (C(3v)), C(46)H(12) (C(2v)), were investigated. Molecular dynamic simulations (MDSs) indicate that the molecules preserve their bonding frame for temperatures up to 300 K (simulation time 100 ps), and maintain atomic cohesion for at least 4 ps at temperatures up to 3500 K. The infrared spectra of the C(60)-derived nanobaskets were simulated through density functional theory (DFT) calculations, allowing for the attribution of infrared signatures specific to each carbon nanobasket. The possibility of using C(60)-derived nanobaskets as molecular containers is demonstrated by performing a DFT study of their bonding to hydrogen, water, and L-alanine. The carbon nanostructures presented here show a higher bonding energy (approximately 1.0 eV), suggesting that a family of nanostructures, C(n)-derived (n = 60,70,76,80, etc) nanobaskets, could work as molecular containers, paving the way for future developments such as tunable traps for complex molecular systems. PMID:19724106

  5. The influence of distribution of hydroxyl groups on vibrational spectra of fullerenol C60(OH)24 isomers: DFT study.

    PubMed

    Dawid, A; Górny, K; Gburski, Z

    2015-02-01

    The infrared and Raman spectra of C60(OH)24 molecule with uniform and non-uniform distribution of hydroxyl groups have been investigated using first principle DFT calculations at the B3LYP/6-31G(d,p) level of theory. The important features of the obtained geometries have been measured and compared to experimental results. The reference calculations of C60 molecule geometry and vibrational spectra have been made and compared to available experimental data. The striking differences of infrared spectra between C60(OH)24 molecule with uniform and non-uniform distribution of hydroxyl groups have been shown and discussed. The OH modes have been identified as the most sensitive to C60(OH)24 isomer configuration. The C-C stretching modes in the Raman spectra of the C60(OH)24 molecule have been found as a potential sensor of OH groups distribution over fullerene C60 surface. PMID:25223813

  6. A theoretical study of the ozonolysis of C60: primary ozonide formation, dissociation, and multiple ozone additions.

    PubMed

    Chapleski, Robert C; Morris, John R; Troya, Diego

    2014-04-01

    We present an investigation of the reaction of ozone with C60 fullerene using electronic structure methods. Motivated by recent experiments of ozone exposure to a C60 film, we have characterized stationary points in the potential energy surface for the reactions of O3 with C60 that include both the formation of primary ozonide and subsequent dissociation reactions of this intermediate that lead to C-C bond cleavage. We have also investigated the addition of multiple O3 molecules to the C60 cage to explore potential reaction pathways under the high ozone flux conditions used in recent experiments. The lowest-energy product of the reaction of a single ozone molecule with C60 that results in C-C bond breakage corresponds to an open-cage C60O3 structure that contains ester and ketone moieties at the seam. This open-cage product is of much lower energy than the C60O + O2 products identified in prior work, and it is consistent with IR experimental spectra. Subsequent reaction of the open-cage C60O3 product with a second ozone molecule opens a low-energy reaction pathway that results in cage degradation via the loss of a CO2 molecule. Our calculations also reveal that, while full ozonation of all bonds between hexagons in C60 is unlikely even under high ozone concentration, the addition of a few ozone molecules to the C60 cage is favorable at room temperature. PMID:24549406

  7. Molecular dynamics and the phase transition in solid C60

    NASA Astrophysics Data System (ADS)

    Tycko, R.; Dabbagh, G.; Fleming, R. M.; Haddon, R. C.; Makhija, A. V.; Zahurak, S. M.

    1991-09-01

    The molecular reorientational dynamics in two phases of solid C60 with C-13 NMR measurements are characterized. A change in the nature of the dynamics, indicated by a change in kinetic parameters extracted from spin-lattice relaxation data, occurs at the phase transition at 260 K. Above the transition, the molecules appear to execute continuous rotational diffusion; below the transition, they appear to jump between symmetry-equivalent orientations. This interpretation is consistent with the X-ray-diffraction results of Heiney et al. (1991) as well as the NMR relaxation and spectral data.

  8. Energy spectrum of C60 fullerene

    NASA Astrophysics Data System (ADS)

    Mironov, G. I.; Murzashev, A. I.

    2011-11-01

    The energy spectrum of the C60 fullerene has been calculated in terms of the Shubin-Vonsovskii-Hubbard model using an approximation of static fluctuations. Based on the spectrum, the optical absorption bands at 4.84, 5.88, and 6.30 eV observed experimentally have been successfully explained. It has been concluded that the model used is applicable for the calculation of the energy spectrum and the energy properties of other nanosystems, such as fullerenes of higher orders, carbon nanotubes, and grafen planes.

  9. Enhanced photoluminescence of C 60 incorporated into interlayers of hydrotalcite

    NASA Astrophysics Data System (ADS)

    Ding, Weiping; Gu, Gang; Zhong, Wei; Zang, Wen-Cheng; Du, Youwei

    1996-11-01

    Strong photoluminescence of sodium-reduced C 60 incorporated into interlayers of hydrotalcite is observed. This phenomenon is correlated to the fact that the reduced C 60 is positioned between positively charged layers of the anion clay. The interaction between the layers and reduced C 60 alters the photophysical properties of C 60 and relaxes the electron transition inhibition, thus enhancing photoluminescence.

  10. Identification of More Interstellar C60+ Bands

    NASA Astrophysics Data System (ADS)

    Walker, G. A. H.; Bohlender, D. A.; Maier, J. P.; Campbell, E. K.

    2015-10-01

    Based on gas-phase laboratory spectra at 6 K, Campbell et al. confirmed that the diffuse interstellar bands (DIBs) at 9632.7 and 9577.5 Å are due to absorption by the fullerene ion {{{C}}}60+. They also reported the detection of two other, weaker bands at 9428.5 and 9365.9 Å. These lie in spectral regions heavily contaminated by telluric water vapor lines. We acquired CFHT ESPaDOnS spectra of HD 183143 close to the zenith and chopped with a nearby standard to correct for the telluric line absorption which enabled us to detect a DIB at 9365.9 Å of relative width and strength comparable to the laboratory absorption. There is a DIB of similar strength and FWHM at 9362.5 Å. A stellar emission feature at 9429 Å prevented detection of the 9428.5 Å band. However, a CFHT archival spectrum of HD 169454, where emission is absent at 9429 Å, clearly shows the 9428.5 Å DIB with the expected strength and width. These results further confirm {{{C}}}60+ as a DIB carrier. Based on observations obtained at the Canada-France-Hawaii Telescope (CFHT), which is operated by the National Research Council of Canada, the Institut National des Sciences de l’Univers of the Centre National de la Recherche Scientifique of France, and the University of Hawaii.

  11. Two-dimensional van der Waals C60 molecular crystal

    PubMed Central

    Reddy, C. D.; Gen Yu, Zhi; Zhang, Yong-Wei

    2015-01-01

    Two-dimensional (2D) atomic crystals, such as graphene and transition metal dichalcogenides et al. have drawn extraordinary attention recently. For these 2D materials, atoms within their monolayer are covalently bonded. An interesting question arises: Can molecules form a 2D monolayer crystal via van der Waals interactions? Here, we first study the structural stability of a free-standing infinite C60 molecular monolayer using molecular dynamic simulations, and find that the monolayer is stable up to 600 K. We further study the mechanical properties of the monolayer, and find that the elastic modulus, ultimate tensile stress and failure strain are 55–100 GPa, 90–155 MPa, and 1.5–2.3%, respectively, depending on the stretching orientation. The monolayer fails due to shearing and cavitation under uniaxial tensile loading. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the monolayer are found to be delocalized and as a result, the band gap is reduced to only 60% of the isolated C60 molecule. Interestingly, this band gap can be tuned up to ±30% using strain engineering. Owing to its thermal stability, low density, strain-tunable semi-conducting characteristics and large bending flexibility, this van der Waals molecular monolayer crystal presents aplenty opportunities for developing novel applications in nanoelectronics. PMID:26183501

  12. Two-dimensional van der Waals C60 molecular crystal

    NASA Astrophysics Data System (ADS)

    Reddy, C. D.; Gen Yu, Zhi; Zhang, Yong-Wei

    2015-07-01

    Two-dimensional (2D) atomic crystals, such as graphene and transition metal dichalcogenides et al. have drawn extraordinary attention recently. For these 2D materials, atoms within their monolayer are covalently bonded. An interesting question arises: Can molecules form a 2D monolayer crystal via van der Waals interactions? Here, we first study the structural stability of a free-standing infinite C60 molecular monolayer using molecular dynamic simulations, and find that the monolayer is stable up to 600 K. We further study the mechanical properties of the monolayer, and find that the elastic modulus, ultimate tensile stress and failure strain are 55-100 GPa, 90-155 MPa, and 1.5-2.3%, respectively, depending on the stretching orientation. The monolayer fails due to shearing and cavitation under uniaxial tensile loading. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the monolayer are found to be delocalized and as a result, the band gap is reduced to only 60% of the isolated C60 molecule. Interestingly, this band gap can be tuned up to ±30% using strain engineering. Owing to its thermal stability, low density, strain-tunable semi-conducting characteristics and large bending flexibility, this van der Waals molecular monolayer crystal presents aplenty opportunities for developing novel applications in nanoelectronics.

  13. DFT study of hydrogen storage in Pd-decorated C60 fullerene

    NASA Astrophysics Data System (ADS)

    El Mahdy, A. M.

    2015-11-01

    Hydrogen storage reactions on Pd-doped C60 fullerene are investigated by using the state-of-the-art density functional theory calculations. The Pd atom prefers to bind at the bridge site between two hexagonal rings, and can bind up to four hydrogen molecules with average adsorption energies of 0.61, 0.45, 0.32, and 0.21 eV per hydrogen molecule. With no metal clustering, the system gravimetric capacities are expected to be as large as 5.8 wt%. While the desorption activation barriers of the complexes nH2 + Pd-C60 with n = 1 are outside the department of energy (DOE) domain (-0.2 to -0.6 eV), the desorption activation barriers of the complexes nH2 + Pd-C60 with n = 2-4 are inside this domain. While the interaction of 1H2 with Pd + C60 is irreversible at 459 K, the interaction of 2H2 with Pd + C60 is reversible at 529 K. The hydrogen storage of the irreversible 1H2 + Pd-C60 and reversible 2H2 + Pd-C60 interactions are characterised in terms of densities of states, infrared, Raman, and proton magnetic resonance spectra, electrophilicity, and statistical thermodynamic stability.

  14. Modulation of nanocavity plasmonic emission by local molecular states of C60 on Au(111).

    PubMed

    Geng, Feng; Zhang, Yang; Yu, Yunjie; Kuang, Yanmin; Liao, Yuan; Dong, Zhenchao; Hou, Jianguo

    2012-11-19

    We investigate the modulation of C60 monolayers on the nanocavity plasmonic (NCP) emission on Au(111) by tunneling electron excitation from a scanning tunneling microscope (STM) tip. STM induced luminescence spectra show not only suppressed emission, but also significant redshift of NCP emission bands on the C60 molecules relative to the bare metal surface. The redshift, together with the bias- and coverage-dependent emission feature, indicates that the C60 molecules act beyond a pure dielectric spacer, their electronic states are heavily involved in the inelastic tunneling process for plasmonic emission. A modified quantum cutoff relation is proposed to explain qualitatively the observed emission feature at both bias polarities. We also demonstrate molecularly resolved optical contrast on the C60 monolayer and discuss the contrast mechanism briefly. PMID:23187525

  15. Orientation-Dependent C60 Electronic Structures Revealed byPhotoemission Spectroscopy

    SciTech Connect

    Brouet, V.; Yang, W.L.; Zhou, X.J.; Choi, H.J.; Louie, S.G.; Cohen, M.L.; Goldoni, A.; Parmigiani, F.; Hussain, Z.; Shen, Z.X.

    2004-11-05

    We observe, with angle-resolved photoemission, a dramatic change in the electronic structure of two C60 monolayers, deposited,respectively, on Ag (111) and (100) substrates, and similarly doped with potassium to half filling of the C60 lowest unoccupied molecular orbital.The Fermi surface symmetry, the bandwidth, and the curvature of the dispersion at Gamma point are different. Orientations of the C60molecules on the two substrates are known to be the main structural difference between the two monolayers, and we present new band-structure calculations for some of these orientations. We conclude that orientations play a key role in the electronic structure of fullerides.

  16. Tuning the conductance of H2O@C60 by position of the encapsulated H2O

    NASA Astrophysics Data System (ADS)

    Zhu, Chengbo; Wang, Xiaolin

    2015-12-01

    The change of conductance of single-molecule junction in response to various external stimuli is the fundamental mechanism for the single-molecule electronic devices with multiple functionalities. We propose the concept that the conductance of molecular systems can be tuned from inside. The conductance is varied in C60 with encapsulated H2O, H2O@C60. The transport properties of the H2O@C60-based nanostructure sandwiched between electrodes are studied using first-principles calculations combined with the non-equilibrium Green’s function formalism. Our results show that the conductance of the H2O@C60 is sensitive to the position of the H2O and its dipole direction inside the cage with changes in conductance up to 20%. Our study paves a way for the H2O@C60 molecule to be a new platform for novel molecule-based electronics and sensors.

  17. Tuning the conductance of H2O@C60 by position of the encapsulated H2O

    PubMed Central

    Zhu, Chengbo; Wang, Xiaolin

    2015-01-01

    The change of conductance of single-molecule junction in response to various external stimuli is the fundamental mechanism for the single-molecule electronic devices with multiple functionalities. We propose the concept that the conductance of molecular systems can be tuned from inside. The conductance is varied in C60 with encapsulated H2O, H2O@C60. The transport properties of the H2O@C60-based nanostructure sandwiched between electrodes are studied using first-principles calculations combined with the non-equilibrium Green’s function formalism. Our results show that the conductance of the H2O@C60 is sensitive to the position of the H2O and its dipole direction inside the cage with changes in conductance up to 20%. Our study paves a way for the H2O@C60 molecule to be a new platform for novel molecule-based electronics and sensors. PMID:26643873

  18. Tuning the conductance of H2O@C60 by position of the encapsulated H2O.

    PubMed

    Zhu, Chengbo; Wang, Xiaolin

    2015-01-01

    The change of conductance of single-molecule junction in response to various external stimuli is the fundamental mechanism for the single-molecule electronic devices with multiple functionalities. We propose the concept that the conductance of molecular systems can be tuned from inside. The conductance is varied in C60 with encapsulated H2O, H2O@C60. The transport properties of the H2O@C60-based nanostructure sandwiched between electrodes are studied using first-principles calculations combined with the non-equilibrium Green's function formalism. Our results show that the conductance of the H2O@C60 is sensitive to the position of the H2O and its dipole direction inside the cage with changes in conductance up to 20%. Our study paves a way for the H2O@C60 molecule to be a new platform for novel molecule-based electronics and sensors. PMID:26643873

  19. EPR study of radical reactions of C 60 dimer connected by a silicon bridge and single bond (C 60SiPh 2C 60)

    NASA Astrophysics Data System (ADS)

    Tumanskii, B. L.; Kalina, O. G.; Sokolov, V. I.; Chistyakov, A. L.; Stankevich, I. V.; Han, A.; Murata, Y.; Komatsu, K.

    2004-09-01

    Radical reactions of C 60 dimer connected by a silicon bridge and single bond (C 60SiPh 2C 60) were studied by EPR-spectroscopy. Attack of phosphoryl radicals or 2,2,6,6-tetramethylpiperidine- N-oxyl on the silicon atom leads to radical substitution of the fullerene and formation of a new fullerenyl radical, the structure of the former being confirmed by quantum-chemical calculations (DFT). The formation of only one type of spin-adduct on addition of phosphoryl radicals to the fullerene core is associated with small distortion of the fullerene cage in C 60SiPh 2C 60. Geometry of fullerene core in dimer differs only slightly from C 60 owing probably to flexibility of Si-C and C-C bonds which share a five-membered ring.

  20. Probing Exciton Diffusion and Dissociation in Single-Walled Carbon Nanotube-C60 Heterojunctions.

    PubMed

    Dowgiallo, Anne-Marie; Mistry, Kevin S; Johnson, Justin C; Reid, Obadiah G; Blackburn, Jeffrey L

    2016-05-19

    The efficiency of thin-film organic photovoltaic (OPV) devices relies heavily upon the transport of excitons to type-II heterojunction interfaces, where there is sufficient driving force for exciton dissociation and ultimately the formation of charge carriers. Semiconducting single-walled carbon nanotubes (SWCNTs) are strong near-infrared absorbers that form type-II heterojunctions with fullerenes such as C60. Although the efficiencies of SWCNT-fullerene OPV devices have climbed over the past few years, questions remain regarding the fundamental factors that currently limit their performance. In this study, we determine the exciton diffusion length in the C60 layer of SWCNT-C60 bilayer active layers using femtosecond transient absorption measurements. We demonstrate that hole transfer from photoexcited C60 molecules to SWCNTs can be tracked by the growth of narrow spectroscopic signatures of holes in the SWCNT "reporter layer". In bilayers with thick C60 layers, the SWCNT charge-related signatures display a slow rise over hundreds of picoseconds, reflecting exciton diffusion through the C60 layer to the interface. A model based on exciton diffusion with a Beer-Lambert excitation profile, as well as Monte Carlo simulations, gives the best fit to the data as a function of C60 layer thickness using an exciton diffusion length of approximately 5 nm. PMID:27127916

  1. Polymeric fullerene chains in RbC60 and KC60

    NASA Astrophysics Data System (ADS)

    Stephens, Peter W.; Bortel, G.; Faigel, G.; Tegze, M.; Jánossy, A.; Pekker, S.; Oszlanyi, G.; Forró, L.

    1994-08-01

    NEARLY all of the molecular crystals containing C60, formed at ambient pressure1,2 have inter-fullerene separations of the order of 10 Å - the expected distance based on the molecular van der Waals radii. The sole exceptions are the room-temperature phases of AC60 (where A denotes K, Rb or Cs), which are formed by reversible solid-state transformation from high-temperature (>150 °C) phases3. These phases have lattice parameters about 9% shorter in one direction, and in addition RbC60 has magnetic properties suggestive of a one-dimensional metal4. We suggested in ref. 4 that this short distance may be due to covalent bonding between neighbouring C60 molecules. Here we provide direct evidence for such bonding from powder X-ray diffraction studies of RbC60 and KC60 . The linkage is through a [2+2] cycloaddition, which has been hypothesized to take place during photopolymerization of solid C60 (ref. 5), and which has also been proposed6 for RbC60. Such inter-fullerene linkages are calculated7,8 to be the preferred mode of dimerization of C60. The AC60 phases thus provide an example of a thermal phase transition driven by the reversible formation and breaking of covalent bonds.

  2. IR, NIR, and UV Absorption Spectroscopy of C60(2+) and C60(3+) in Neon Matrixes.

    PubMed

    Kern, Bastian; Strelnikov, Dmitry; Weis, Patrick; Böttcher, Artur; Kappes, Manfred M

    2014-02-01

    C60(2+) and C60(3+) were produced by electron-impact ionization of sublimed C60 and charge-state-selectively codeposited onto a gold mirror substrate held at 5 K together with neon matrix gas containing a few percent of the electron scavengers CO2 or CCl4. This procedure limits charge-changing of the incident fullerene projectiles during matrix isolation. IR, NIR, and UV-vis spectra were then measured. Ten IR absorptions of C60(2+) were identified. C60(3+) was observed to absorb in the NIR region close to the known vibronic bands of C60(+). UV spectra of C60, C60(+), and C60(2+) were almost indistinguishable, consistent with a plasmon-like nature of their UV absorptions. The measurements were supported by DFT and TDDFT calculations, revealing that C60(2+) has a singlet D5d ground state whereas C60(3+) forms a doublet of Ci symmetry. The new results may be of interest regarding the presence of C60(2+) and C60(3+) in space. PMID:26276592

  3. Light-Initiated Transformation of C60 Clusters in Water

    EPA Science Inventory

    Although Buckminster fullerene (C60) has an extremely low water solubility (~8 ng/L), the formation of stable clusters (aqu/nC60) not only greatly increases the mass of C60 dispersed in water, but also alters its physicochemical properties. This research focused on investigating ...

  4. Investigation of Photochemical Properties of C60 Aggregates in Water

    EPA Science Inventory

    As an emerging new material with unique structure and properties, the behavior and fate of Buckminster fullerene (C60) in natural waters has gained increasing attention. Although the water solubility of C60 is extremely low, the formation of C60 aggregates in water could alter th...

  5. Retention of Aqu/C60 Nanoparticles on Quartz Surfaces

    EPA Science Inventory

    Studies have shown that C60 fullerene can form stable suspensions of colloidal sized particles in water resulting in C60 aqueous concentrations many orders of magnitude above C60’s aqueous solubility. These studies have raised concern over the mobility and distribution of fuller...

  6. The Curators of the University of Missouri Modeling the Infrared Emission of C_60 in Space

    NASA Astrophysics Data System (ADS)

    Li, Aigen

    Fullerenes are cage-like molecules of pure carbon, such as C_60, C_70, C_76, and C_84. C_60, also known as buckminsterfullerene, is the most stable fullerene and has a soccer- ball like structure. The presence of fullerenes in space has been suggested and observationally explored since their first synthesis in the laboratory in 1985 by Harry Kroto and his colleagues which earned them the 1996 Nobel prize in chemistry. C_60 (as well as C_70) has recently been detected in reflection nebulae, post-AGB stars, protoplanetary nebulae, planetary nebulae, Herbig Ae/Be stars, and young stellar objects through their characteristic infrared emission bands. The formation of C_60 in interstellar and circumstellar environments is not firmly established. Experimental studies have shown that C_60 can be made by gas-phase condensation (e.g. through vaporization of graphite) in a hydrogen-poor environment. In view of the simultaneous detection of C_60 and PAHs in hydrogen-rich interstellar and circumstellar regions, it has also been suggested that C_60 could be generated by the decomposition of hydrogenated amorphous carbon, or the destruction of PAHs, both induced by shocks and/or UV photoprocessing. The phase (gas or solid) and excitation mechanism of C_60 in interstellar and circumstellar conditions are also hotly debated in the literature. One model suggests that C_60 is attached to dust and emits in solid-phase at the equilibrium temperature of the dust. Another model suggests that C_60 is stochastically excited by UV photons and emits in the gas-phase. We prefer the latter model as in interstellar and circumstellar conditions the energy content of a C_60 molecule is often smaller than the energy of a single starlight photon and C_60 is expected to undergo stochastical heating. We propose a two-year project to model the vibrational excitation of C_60 and calculate its infrared emission spectra in a wide variety of regions (e.g. reflection nebulae excited by stars of a range of

  7. Advanced carbon-based material C60 modification using partially ionized cluster and energetic beams

    NASA Astrophysics Data System (ADS)

    Yuancheng, Du; Zhongmin, Ren; Zhifeng, Ying; Ning, Xu; Fuming, Li

    1997-06-01

    Two processes have been undertaken using Partially ionized cluster deposition (PICBD) and energetic ion bombardment beams deposition (IBD) respectively. C60 films deposited by PICBD at V=0 and 65 V, which result in highly textured close-packed structure in orientation (110) and being more polycrystalline respectively, the resistance of C60 films to oxygen diffusion contamination will be improved. In the case of PICBD, the ionized C60 soccer-balls molecules in the evaporation beams will be fragmented in collision with the substrate under the elevated accelerating fields Va. As a new synthetic IBD processing, two low energy (400 and 1000 eV) nitrogen ion beams have been used to bombard C60 films to synthesize the carbon nitride films.

  8. Structural transitions of SWNT filled with C60 under high pressure

    NASA Astrophysics Data System (ADS)

    Yong-gang, Zou; Li, Xu; Kun, Tian; He, Zhang; Xiao-hui, Ma; Ming-guang, Yao

    2016-05-01

    Raman spectra of C60 filled single-walled carbon nanotubes (C60@SWNTs) with diameters of 1.3–1.5 nm have been studied under high pressure. A plateau in the pressure dependence of the G-band frequency at around 10 GPa was observed in both experiments with 514 nm and 830 nm excitation lasers, which is similar to the high pressure behaviors of pristine SWNTs. This structural transition has been assigned to the transformation into a peanut-like structure of the nanotubes. At pressure below 2 GPa, no obvious Raman signature related to the structural transition of nanotubes was observed, unlike what has been reported for C70 filled nanotubes. We discussed this point in terms of the arrangement differences of C60 and C70 molecules inside the nanotubes. At higher pressure up to 15 GPa, a graphite-like pressure evolution was observed in our C60@SWNTs.

  9. Screening of C60 crystallization using a microfluidic system.

    PubMed

    Shinohara, Kyosuke; Fukui, Takeshi; Abe, Hiroaki; Sekimura, Naoto; Okamoto, Koji

    2006-07-18

    We have carried out screening of C60 crystallization using a simple liquid/liquid interfacial precipitation method in a microfluidic device. By controlling the time, temperature, and concentration, various metastable phases of C60 crystals were found, including tubes, spheres, open-ended hollow columns, stars, branches, and trees. The obtained C60 crystal shapes are similar to those of snow crystals. These findings suggest an urgent need to screen C60 crystallization for the development of fullerene C60 drugs. PMID:16830986

  10. Colloidal Properties of Aqueous Fullerenes: Isoelectric Points and Aggregation Kinetics of C60 and C60 Derivatives

    EPA Science Inventory

    Aqueous colloidal suspensions of C-60 (aqu/C-60) and the C-60 derivatives PCBM ([6,6]-phenyl C-61-butyric acid methyl ester) and the corresponding butyl and octyl esters, PCBB and PCBO (aqu/PCB-R, where R is an alkyl group), were produced by stirring in double deionized water for...

  11. C60 fullerenes from combustion of common fuels.

    PubMed

    Tiwari, Andrea J; Ashraf-Khorassani, Mehdi; Marr, Linsey C

    2016-03-15

    Releases of C60 fullerenes to the environment will increase with the growth of nanotechnology. Assessing the potential risks of manufactured C60 requires an understanding of how its prevalence in the environment compares to that of natural and incidental C60. This work describes the characterization of incidental C60 present in aerosols generated by combustion of five common fuels: coal, firewood, diesel, gasoline, and propane. C60 was found in exhaust generated by all five fuels; the highest concentrations in terms of mass of C60 per mass of particulate matter were associated with diesel and coal. Individual aerosols from these combustion processes were examined by transmission electron microscopy. No relationship was found between C60 content and either the separation of graphitic layers (lamellae) within the particles, nor the curvature of those lamellae. Estimated global emissions of incidental C60 to the atmosphere from coal and diesel combustion range from 1.6 to 6.3 t yr(-1), depending upon combustion conditions. These emissions may be similar in magnitude to the total amount of manufactured C60 produced on an annual basis. Consequent loading of incidental C60 to the environment may be several orders of magnitude higher than has previously been modeled for manufactured C60. PMID:26789363

  12. Characterization of the intercalate C60(CO2)x by powder neutron diffraction

    NASA Astrophysics Data System (ADS)

    James, M.; Kennedy, S. J.; Elcombe, M. M.; Gadd, G. E.

    1998-12-01

    The intercalate compound C60(CO2)x has been synthesized by hot isostatically pressing C60 under 170 MPa of CO2 and 350 °C. Neutron powder diffraction studies conducted on C60(CO2)x between room temperature and 5 K have been analyzed using Rietveld techniques and reveal a structural transition between a high-temperature (>~250 K) face-centered cubic phase [Fm3¯m, a=14.224(2) Å (293 K)] and a low-temperature (<~150 K) monoclinic phase [P21/n, a=9.7438(9) Å, b=9.7473(9) Å, c=14.6121(11) Å, β=90.390(6)° (5 K)]. The CO2 molecules occupy the octahedral interstices between the C60 molecules and are oriented along the body diagonal of the high-temperature phase. In the low-temperature phase they are tilted slightly away from the c axis so as to place the oxygen atoms adjacent to the center of a pentagonal face on the C60 molecules.

  13. Buckminsterfullerene C60 — a surface with curvature and interesting properties

    NASA Astrophysics Data System (ADS)

    Rosén, Arne; Wästberg, Bo

    1992-05-01

    Molecular cluster calculations within the local density approximation have been performed in a study of the electronic structure of the truncated icosahedral C60 also known as "Buckminsterfullerene" and C60 doped with K, B and N. Evaluated ionisation energies for C60 are found to be in good agreement with recently observed gas phase and solid-state photoelectron spectra. Excitation energies evaluated in the 1-10 eV energy range are also found to reproduce UV, IR and HREELS spectra. Calculations for the KC60 molecule, with the K atom located at the centre of the cage, show how the valence electron from K is transferred to the LUMO state of the bare C60 molecule. Doping with a B or N atom in the centre of the cage creates a different structure with a partly occupied level in the band gap, similar to the donor and acceptor levels in traditionally doped semiconductors. Doping by substitution of two of the carbon atoms in the cage with X = B or N, as modelled with the C58X2 cluster, gives a different structure with a splitting of the HOMO and LUMO levels in the bare C60 molecule.

  14. Role of electron energy loss in modification of C60 thin films by swift heavy ions

    NASA Astrophysics Data System (ADS)

    Bajwa, Navdeep; Ingale, Alka; Avasthi, D. K.; Kumar, Ravi; Tripathi, A.; Dharamvir, Keya; Jindal, V. K.

    2008-09-01

    This paper presents a comparative study of the effects of irradiation by swift heavy ions (SHIs) with Se values ranging from 80 to 1270 eV/Å and fluence ranges varying between 1010 and 1014 ions/cm2 incident on thin films of C60. The control over Se is exercised through the choice of ion species for irradiation (O, Ni, and Au). Structural changes in C60 were investigated quantitatively using Raman spectroscopy. The results indicate that at low fluences polymer formation takes place whereas at high fluences there is complete fragmentation of C60, resulting in amorphous carbon formation. Measured values of band gap and in situ resistivity decrease with fluence. This result is consistent with the structural modifications observed by Raman spectroscopy. The composition of the polymer fraction formed (e.g., the content of two dimensional polymerized network of C60 molecules) as well as that of a-C (e.g., the content of nanographite) also vary with Se of the ion used. A phenomenological model, taking into account the ion track, enables us to explain the trend of polymer formation as well as fragmentation of C60, with increasing fluence of SHI. The cross section for damage (fragmentation of C60 molecules) has two values—one effective at low fluences and the other at high fluences. By arriving at a quantitative formula giving the fraction of polymer/damaged C60 molecules at any given fluence, we are able to predict the fluence and ion species required for a given amount of polymerization/damage or vice versa. Effort has been made to correlate Se and Sn values to the damage cross sections using data from this work along with those from other experiments using keV and MeV ions.

  15. Metal-oxide-semiconductor diodes containing C60 fullerenes for non-volatile memory applications

    NASA Astrophysics Data System (ADS)

    Beckmeier, Daniel; Baumgärtner, Hermann

    2013-01-01

    For non-volatile memories, silicon-oxide-nitride-oxide-silicon or floating gate structures are used to store information by charging and discharging electronic states reversibly. In this article, we propose to replace the floating gate by C60 molecules. This would allow more defined programming voltages because of the discrete molecular energy levels and a higher resistance to tunneling oxide defects because of the weak electrical connection between the single molecules. Such C60 MOS diode structures are produced and their electrical properties are analyzed regarding current transport and charging mechanism of the molecules. To create the MOS structures, C60 molecules (5% of a monolayer) are evaporated onto a part of a clean silicon wafer and covered by amorphous silicon in situ in an ultra high vacuum system. Then the wafer is oxidized in wet atmosphere at just 710 °C through the C60 layer. The goal is to produce a clean oxide above and under the molecules without destroying them. Aluminum gate contacts are defined on top of these layers to perform complementary capacitance voltage (CV) and current voltage (IV) measurements. First, the gate voltage is swept to analyze the injection current, then CV measurements are performed after each sweep to analyze the charge state of the C60 layer and the oxide quality. Reference diodes without C60 on the same wafer show an identical Fowler-Nordheim (FN) tunneling behavior for currents injected from silicon or from aluminum, respectively. In the CV curves, no pronounced flatband voltage shift is observable. In diodes with C60, for negative gate voltages, a classical FN tunneling is observed and compared to theory. The electron injection from silicon shows a different tunneling current behavior. It starts at a lower electric field and has a smaller slope then a FN current would have. It is identified as a trap-assisted tunneling (TAT) current caused by oxidation-induced traps under the C60 layer. It is modeled by an

  16. Electron Impact Excitation of C60 Adducts: Flourescence From C60OH and C60H Species

    NASA Technical Reports Server (NTRS)

    Trajmar, S.; Kanik, I.

    1996-01-01

    An investigation concerning possible visible and UV photon emissions by gas phase C(sub 60) ( and C(sub 70)) samples under electron impact excitation was caried out in the 180-750 nm spectral region. Radiation resembling OH (A (sup 2)pi {leads to}X (sup 2){summation}) emission bands and H Balmer series was observed. Based on our investigations, it is concluded that none of the observed emission was associated with the fullerene molecule itself but with the C(sub 60)OH and C(sub 60)H adducts (which are present in the fullerene samples). We also conclude that in these adducts, simultaneous ionization and excitation take place under electron impact and the excited ionic species (C(sub 60)+OH* and C(sub 60)+H*) decay by radiation which was observed in our experiments. These surprising results reveal an interesting new character of buckyball adducts.

  17. Carbon Nanotubes Investigated by N@C60 and N@C70 Spin Probes

    NASA Astrophysics Data System (ADS)

    Corzilius, B.; Gembus, A.; Dinse, K.-P.; Simon, F.; Kuzmany, H.

    2005-09-01

    Nitrogen atoms encapsulated in C60 can be used to detect small deviations from spherical symmetry via deformation-induced non-vanishing Zero-Field-Splitting (ZFS). In this context, experiments were performed by using these electronic quartet spin probes to investigate single wall carbon nanotubes. Time-fluctuating ZFS interaction would be indicative for rotational and/or translational degrees of freedom. Using pulsed EPR techniques, spin relaxation rates of N@C60 and also of N@C70 molecules with inherent static ZFS were measured. The analysis of their temperature dependence gave information about the dynamics of N@C60 and N@C70 molecules confined to the inside of the tubes.

  18. Direct patterning of a cyclotriveratrylene derivative for directed self-assembly of C60

    NASA Astrophysics Data System (ADS)

    Osner, Zachary R.; Nyamjav, Dorjderem; Holz, Richard C.; Becker, Daniel P.

    2011-07-01

    A novel apex-modified cyclotriveratrylene (CTV) derivative with an attached thiolane-containing lipoic acid linker was directly patterned onto gold substrates via dip-pen nanolithography (DPN). The addition of a dithiolane-containing linker to the apex of CTV provides a molecule that can adhere to a gold surface with its bowl-shaped cavity directed away from the surface, thereby providing a surface-bound CTV host that can be used for the directed assembly of guest molecules. Subsequent exposure of these CTV microarrays to C60 in toluene resulted in the directed assembly of predesigned, spatially controlled, high-density microarrays of C60. The molecular recognition capabilities of this CTV template toward C60 provides proof-of-concept that supramolecular CTV scaffolds can be directly patterned onto surfaces providing a foundation for the development of organic electronic and optoelectronic materials.

  19. Interfacial and intermolecular interactions determining the rotational orientation of C60 adsorbed on Au(111)

    NASA Astrophysics Data System (ADS)

    Paßens, Michael; Karthäuser, Silvia

    2015-12-01

    Close-packed monolayers of fullerenes on metallic substrates are very rich systems with respect to their rotational degrees of freedom and possible interactions with different adsorption sites or next neighbours. In this connection, we report in detail on the (2√3 × 2√3)R30°-superstructure of C60 with respect to the Au(111)-surface. We use molecular orbital imaging in systematic UHV-STM studies to reveal the delicate balance of interfacial and intermolecular interactions in this system. Thus, bright C60-molecules in 5:6-top and 6:6-top geometries are observed depending on the respective next neighbours. Moreover, tiny changes in the appearance of the unoccupied molecular orbitals of dim C60-molecules in hex-vac positions are identified which are caused by the respective interaction with the facets surrounding the Au-vacancy.

  20. Electronic Pair-Binding and Hund's Rule Violations in Doped C60

    NASA Astrophysics Data System (ADS)

    Jiang, Hong-Chen; Kivelson, Steven

    We calculate the electronic properties of the t-J model on a C60 molecule using the density-matrix renormalization group and show that Hund's first rule is violated and that for an average of three added electron per molecule, an effective attraction (pair-binding) arises for intermediate values of t=J. Specifically, it is energetically favorable to put four electrons on one C60 and two on a second rather than putting three on each. Our results show that a dominantly electronic mechanism of superconductivity is possible in doped C60. HCJ and SAK were supported by the Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division, under Contract DE-AC02-76SF00515.

  1. Film growth and surface reactions of C60 on Si(100)H(2×1)

    NASA Astrophysics Data System (ADS)

    Schmidt, J.; Hunt, M. R. C.; Miao, P.; Palmer, R. E.

    1997-10-01

    High-resolution electron-energy-loss spectroscopy (HREELS) has been used to characterize C60 films up to 4 monolayers thick grown at room temperature on hydrogen-terminated Si(100). Our results show that compared with C60 films on clean Si(100) surfaces a considerably higher degree of order in the as-deposited films is achieved. At low coverages the observed C60 vibrational modes and the Si-H vibrations of the substrate are essentially unshifted, indicating a van der Waals-type interaction between C60 and Si(100)H(2×1). After annealing at 450 K the film order is substantially increased. Annealing at 600 K results in desorption of the C60 multilayers and a hydrogen-transfer reaction from the surface to the adsorbed monolayer molecules. When annealing the sample at 800 K, the remaining surface terminating hydrogen desorbs and evidence for a change in the C60 bonding configuration is found. Finally, flashing the sample at 1300 K leads to the formation of silicon carbide.

  2. C60-DOM interactions and effects on C60 apparent solubility: a molecular mechanics and density functional theory study.

    PubMed

    Wang, Zhuang; Chen, Jingwen; Sun, Qian; Peijnenburg, Willie J G M

    2011-08-01

    Dissolved organic matter (DOM) plays a critical role in the transport of carbon nano-particles (e.g. C(60)) in the aquatic environment. However, the mechanism for C(60)-DOM interactions and its environmental implications needs further investigations. In this study, the interaction of C(60) with relevant reference compounds of DOM (DOM(R)) is computationally simulated by molecular mechanics and density functional theory (DFT). All the C(60)-DOM(R) complexes are firstly optimized by classical annealing, and then DFT using the Dmol(3) code. The adsorption energies of C(60) on DOM(R) were computed. The computed electrostatic potential indicates that DOM(R) are electron acceptors in the C(60)-DOM(R) complexes, and the thermodynamic calculations indicate that electrostatic interaction is the dominant driving force for the C(60)-gallic acid complexation process in water. The presence of DOM(R) increases the apparent water solubility of C(60). It is also observed that the C(60) apparent water solubility decrease with the increase of the energy gaps of frontier molecular orbitals (E(LUMO)-E(HOMO)) for each C(60)-DOM(R) complex. These findings indicate that computational simulation is an important tool for predicting the behavior and fate of carbon nano-particles in the aquatic environment. PMID:21419494

  3. Epitaxial Templating of C60 with a Molecular Monolayer.

    PubMed

    Rochford, L A; Jones, T S; Nielsen, C B

    2016-09-01

    Commensurate epitaxial monolayers of truxenone on Cu (111) were employed to template the growth of monolayer and bilayer C60. Through the combination of STM imaging and LEED analysis we have demonstrated that C60 forms a commensurate 8 × 8 overlayer on truxenone/Cu (111). Bilayers of C60 retain the 8 × 8 periodicity of templated monolayers and although Kagome lattice arrangements are observed these are explained with combinations of 8 × 8 symmetry. PMID:27540868

  4. Preparation of C 60 single crystalline thin film by ionized cluster beam deposition and ion implantation into single crystalline C 60 thin film

    NASA Astrophysics Data System (ADS)

    Isoda, Satoru; Kawakubo, Hiroaki; Nishikawa, Satoshi; Wada, Osamu

    1996-05-01

    We have succeeded in preparing single crystalline C 60 thin film of a lateral extension in the order of several millimeters on mica by ionized cluster beam (ICB) deposition. During the growth process, planar dendrite-like single crystalline islands were observed by an atomic force microscope (AFM). It was concluded from reflection high-energy electron diffraction (RHEED) and transmission electron diffraction (TED) analyses that these islands grow hetero-epitaxially on mica. As the deposition process continues, the single crystalline islands coalesce and finally form a giant single crystal without grain boundaries between the former islands. This layered dendrite-like crystal growth is considered to be due to the ICB process, namely, ionizing molecules and accelerating them. Furthermore, the effect of ion (P +, B +, Ar +) implantation into C 60 thin films on the molecular structure and the conductivity has been studied under various implantation conditions. It was found from the analyses of FT-IR and Raman spectroscopies that the soccer-ball-like structure of C 60 changes into a diamond-like carbon (DLC) structure with an implantation energy higher than 40 keV, whereas the structure undergoes virtually no change with 10 keV implantation. As for conductivity changes under the lower implantation energy condition, the minimum dose of P + ions required to increase the conductivity from the non-doped value (10 12 cm -2) is 10 times lower than in the case of Ar + implantation. The conductivity change for the P + implantation could be explained satisfactorily not only by the effect of chemically-modified C 60 but also by the effect of a charge-transfer state between C 60 and implanted ions. It was concluded from these results that the conductivity of the C 60 film can be controlled over a wide range based on the carrier generation mechanism, which depends on the implantation conditions.

  5. When a nanoparticle meets a superhalogen: a case study with C60 fullerene.

    PubMed

    Sikorska, Celina

    2016-07-28

    The ability of a selected nanoparticle to form stable systems with superhalogens (i.e. AlF4, AlCl4, MgF3, MgCl3, LiF2, LiCl2, and LiI2) is examined on the basis of theoretical considerations supported by ab initio calculations. It is demonstrated that the C60 fullerene molecule should form stable and strongly bound (C60)˙(+)(superhalogen)(-) radical cation salts when combined with an appropriately chosen superhalogen radical (acting as an oxidizing agent). The conclusion is supported by providing: (i) the structural deformation of superhalogens and C60 nanoparticles upon ionization, (ii) predicted charge flow between the fullerene and each superhalogen (which allows estimating the amount of electron density withdrawn from the C60 molecule during the ionization process), (iii) the localization of the spin density distribution, and (iv) the interaction energies for the compounds obtained both at the B3LYP/6-31+G(d) level and at the B3LYP-D3/6-31+G(d) level. Solvent effects have been considered in the present study by means of the polarizable continuum model. It is found that the stability of C60/superhalogen species can be improved in solvents. We believe that the results provided in this contribution may likely be of prospective relevance in the future studies on the issue of binding and removal of this potentially risky nanoparticle. PMID:27346461

  6. Laboratory confirmation of C60(+) as the carrier of two diffuse interstellar bands.

    PubMed

    Campbell, E K; Holz, M; Gerlich, D; Maier, J P

    2015-07-16

    The diffuse interstellar bands are absorption lines seen towards reddened stars. None of the molecules responsible for these bands have been conclusively identified. Two bands at 9,632 ångströms and 9,577 ångströms were reported in 1994, and were suggested to arise from C60(+) molecules (ref. 3), on the basis of the proximity of these wavelengths to the absorption bands of C60(+) measured in a neon matrix. Confirmation of this assignment requires the gas-phase spectrum of C60(+). Here we report laboratory spectroscopy of C60(+) in the gas phase, cooled to 5.8 kelvin. The absorption spectrum has maxima at 9,632.7 ± 0.1 ångströms and 9,577.5 ± 0.1 ångströms, and the full widths at half-maximum of these bands are 2.2 ± 0.2 ångströms and 2.5 ± 0.2 ångströms, respectively. We conclude that we have positively identified the diffuse interstellar bands at 9,632 ångströms and 9,577 ångströms as arising from C60(+) in the interstellar medium. PMID:26178962

  7. Computer simulations of the Adsorption of Xenon onto a C60 monolayer on Ag (111)

    NASA Astrophysics Data System (ADS)

    Gatica, Silvina; Cole, Milton; Diehl, Renee

    2007-03-01

    We performed Grand Canonical Monte Carlo simulations to study the adsorption of Xenon on a substrate composed of C60 molecules placed on top of a Ag(111) surface. The C60 molecules form a commensurate structure at a distance of 0.227 nm above the Ag surface. The interaction potential between the Xe atoms and the substrate has two contributions: from the C60 molecules and from the Ag atoms. In the simulations, the interaction with the Ag surface was computed using an ab initio van der Waals potential, varying as 1/d^3. The interaction between the Xe atoms and each C60 molecule was computed using a potential previously developed by Hernandez et.al. (E. S. Hernandez, M. W. Cole and M. Boninsegni, ``Wetting of spherical surfaces by quantum fluids'', J. Low Temp. Phys. 134, 309-314 (2004)), who integrated the Lennard Jones interaction over the surface of a spherical buckyball. The total potential has especially attractive 3-fold sites, positioned 0.4 nm above the point between each three buckyballs. The low coverage uptake populates those sites, and then continues forming a monolayer. The adsorption isotherms show several steps, typical of substrates that have distinct adsorption sites. We compare the results with the experimental data.

  8. Synthesis and characterization of tetrakis-silylated C60 isomers.

    PubMed

    Maeda, Yutaka; Rahman, G M Aminur; Wakahara, Takatsugu; Kako, Masahiro; Okamura, Mutsuo; Sato, Soichi; Akasaka, Takeshi; Kobayashi, Kaoru; Nagase, Shigeru

    2003-08-22

    A photochemical reaction of C(60) with disilane in a 2:3 ratio affords the isomer mixture of the tetrakis-adduct of C(60)((t)BuPh(2)Si)(4) as the major product. The use of a three-stage HPLC separation system isolated three of their isomers. Their structural assignments were based on FAB mass, UV-vis, NMR, and cyclic voltammetry (CV) measurements. The CV analysis showed that the terakis-adduct has lower oxidation and higher reduction potentials than the bis-adduct C(60)((t)BuPh(2)Si)(2) and the parent C(60). PMID:12919050

  9. Photoexcitation of a volume plasmon in C60 ions

    SciTech Connect

    Scully, S.W.J.; Emmons, E.D.; Gharaibeh, M.F.; Phaneuf, R.A.; Kilcoyne, A.L.D.; Schlachter, A.S.; Schippers, S.; Muller, A.; Chakraborty, H.S.; Madjet, M.E.; Rost, J.M.

    2005-06-21

    Neutral C60 is well known to exhibit a giant resonance in its photon absorption spectrum near 20 eV. This is associated with a surface plasmon, where delocalized electrons oscillate as a whole relative to the ionic cage. Absolute photoionization cross-section measurements for C60(sup+), C60(sup2+), and C60(sup3+) ions in the 17 75eV energy range show an additional resonance near 40 eV. Time-dependent density functional calculations confirm the collective nature of this feature, which is characterized as a dipole-excited volume plasmon made possible by the special fullerene geometry.

  10. Self-assembling of C60-imidazole and C60-pyridine adducts in the Langmuir and Langmuir-Blodgett films via complex formation with water-soluble zinc porphyrins

    NASA Astrophysics Data System (ADS)

    Marczak, Renata; Noworyta, Krzysztof; Kutner, Wlodzimierz; Gadde, Suresh; D'Souza, Francis

    2003-10-01

    The C60-pyridine, C60py, and C60-imidazole, C60im, adducts were found to self-assemble in films floating onto aqueous solutions of zinc tetrakis (N-methylpyridinium)porphyrin cation, Zn(TMPyP), or zinc tetrakis (4-sulfonatophenyl)porphyrin anion, Zn(TPPS). This self assembling was due to axial ligation of the C60 adducts (acceptors) by Zn porphyrins (donors), which lead to the formation of relatively stable donor-acceptor dyads in the water-air interfaces. The films were compressed in a Langmuir trough and characterized by isotherms of surface pressure vs. area per molecule as well as by the Brewster angle microscopy imaging. All systems formed stable aggregated Langmuir films of the "expanded liquid" type. Extensive compression of the films resulted in two-dimensional phase transitions. The area per molecule at infinite dilution of the adducts in films increased in the order: water<0.1 mM Zn(TPPS)<0.1 mM Zn(TPMyP). Comparison of the determined and calculated values of area per molecule indicated that orientation of porphyrins in the complexes was parallel with respect to the interface plane. The Langmuir films were transferred, by using the Langmuir-Blodgett technique, onto quartz slides. The UV-vis spectroscopic study of these films revealed that Zn porphyrins were transferred together with the C60 adducts and that the transfer efficiency increased in the order: C60py-Zn(TPPS)<C60py-Zn(TMPyP)<C60im-Zn(TPPS)<C60im-Zn(TMPyP), i.e., in accord with the increase of stability of the respective dyads in solutions.

  11. Analyses of the Binding between Water Soluble C60 Derivatives and Potential Drug Targets through a Molecular Docking Approach

    PubMed Central

    Liu, Junjun; Zhang, Houjin

    2016-01-01

    Fullerene C60, a unique sphere-shaped molecule consisting of carbon, has been proved to have inhibitory effects on many diseases. However, the applications of C60 in medicine have been severely hindered by its complete insolubility in water and low solubility in almost all organic solvents. In this study, the water-soluble C60 derivatives and the C60 binding protein’s structures were collected from the literature. The selected proteins fall into several groups, including acetylcholinesterase, glutamate racemase, inosine monophosphate dehydrogenase, lumazine synthase, human estrogen receptor alpha, dihydrofolate reductase and N-myristoyltransferase. The C60 derivatives were docked into the binding sites in the proteins. The binding affinities of the C60 derivatives were calculated. The bindings between proteins and their known inhibitors or native ligands were also characterized in the same way. The results show that C60 derivatives form good interactions with the binding sites of different protein targets. In many cases, the binding affinities of C60 derivatives are better than those of known inhibitors and native ligands. This study demonstrates the interaction patterns of C60 derivatives and their binding partners, which will have good impact on the fullerene-based drug discovery. PMID:26829126

  12. C60 chain phases on ZnPc/Ag(111) surfaces: Supramolecular organization driven by competing interactions.

    PubMed

    Jin, W; Liu, Q; Dougherty, D B; Cullen, W G; Reutt-Robey, J E; Weeks, J; Robey, S W

    2015-03-14

    Serpentine chain C60 phases were observed in scanning tunneling microscopy (STM) images of C60 layers on zinc phthalocyanine (ZnPc) or pentacene covered Ag(111) and Au(111) surfaces. This low-density, quasi-one-dimensional organization contrasts starkly with the close-packed hexagonal phases observed for C60 layers on bare metal substrates. STM was employed to perform a detailed investigation of these chain structures for C60/ZnPc/Ag(111) heterolayers. Motivated by the similarity of these chain phases, and the chain and stripe organization occurring in dipole-fluid systems, we investigated a model based on competing van der Waals attractions and electrostatic repulsions between C60 molecules as an explanation for the driving force behind these monolayer phases. Density functional theory (DFT) calculations revealed significant charge transfer to C60 from the Ag(111) substrate, through the intervening ZnPc layer, inducing electrostatic interactions between C60 molecules. Molecular dynamics simulations performed with attractive van der Waals interactions plus repulsive dipole-dipole interactions reproduced the C60 chain phases with dipole magnitudes consistent with DFT calculations. PMID:25770499

  13. C60 chain phases on ZnPc/Ag(111) surfaces: Supramolecular organization driven by competing interactions

    NASA Astrophysics Data System (ADS)

    Jin, W.; Liu, Q.; Dougherty, D. B.; Cullen, W. G.; Reutt-Robey, J. E.; Weeks, J.; Robey, S. W.

    2015-03-01

    Serpentine chain C60 phases were observed in scanning tunneling microscopy (STM) images of C60 layers on zinc phthalocyanine (ZnPc) or pentacene covered Ag(111) and Au(111) surfaces. This low-density, quasi-one-dimensional organization contrasts starkly with the close-packed hexagonal phases observed for C60 layers on bare metal substrates. STM was employed to perform a detailed investigation of these chain structures for C60/ZnPc/Ag(111) heterolayers. Motivated by the similarity of these chain phases, and the chain and stripe organization occurring in dipole-fluid systems, we investigated a model based on competing van der Waals attractions and electrostatic repulsions between C60 molecules as an explanation for the driving force behind these monolayer phases. Density functional theory (DFT) calculations revealed significant charge transfer to C60 from the Ag(111) substrate, through the intervening ZnPc layer, inducing electrostatic interactions between C60 molecules. Molecular dynamics simulations performed with attractive van der Waals interactions plus repulsive dipole-dipole interactions reproduced the C60 chain phases with dipole magnitudes consistent with DFT calculations.

  14. Growth and Potential Damage of Human Bone-Derived Cells Cultured on Fresh and Aged C60/Ti Films

    PubMed Central

    Kopova, Ivana; Lavrentiev, Vasily; Vacik, Jiri; Bacakova, Lucie

    2015-01-01

    Thin films of binary C60/Ti composites, with various concentrations of Ti ranging from ~ 25% to ~ 70%, were deposited on microscopic glass coverslips and were tested for their potential use in bone tissue engineering as substrates for the adhesion and growth of bone cells. The novelty of this approach lies in the combination of Ti atoms (i.e., widely used biocompatible material for the construction of stomatological and orthopedic implants) with atoms of fullerene C60, which can act as very efficient radical scavengers. However, fullerenes and their derivatives are able to generate harmful reactive oxygen species and to have cytotoxic effects. In order to stabilize C60 molecules and to prevent their possible cytotoxic effects, deposition in the compact form of Ti/C60 composites (with various Ti concentrations) was chosen. The reactivity of C60/Ti composites may change in time due to the physicochemical changes of molecules in an air atmosphere. In this study, we therefore tested the dependence between the age of C60/Ti films (from one week to one year) and the adhesion, morphology, proliferation, viability, metabolic activity and potential DNA damage to human osteosarcoma cells (lines MG-63 and U-2 OS). After 7 days of cultivation, we did not observe any negative influence of fresh or aged C60/Ti layers on cell behavior, including the DNA damage response. The presence of Ti atoms resulted in improved properties of the C60 layers, which became more suitable for cell cultivation. PMID:25875338

  15. Electron spin resonance study of Rb xC 60 and K xC 60 powders

    NASA Astrophysics Data System (ADS)

    Feng, S. Q.; Jia, Y. Q.; Zhu, S. L.; Fu, J. S.; Wu, E.; Mao, J. C.; Han, R. S.; Gu, Z. N.; Zhou, X. H.; Jin, Z. X.

    1993-11-01

    Rb and K doped C 60 compounds are prepared by the vapor-solid reaction method. Superconductive shielding fraction is determined as 35-75% for Rb xC 60 and 10% for K xC 60. Electron spin resonance (ESR) measurements in absorption mode are performed in the temperature range of 5-300 K. A strong ESR signal at g=2.002 for Rb xC 60 and g=2.003 for K xC 60 has been observed. The g-value is nearly independent upon temperature for both Rb xC 60 and K xC 60 while the linewidth behaves differently, increasing from 2.0 G at 5 K to 6.0 G at 250 K in Rb xC 60 and remaining constant of 2.3 G in K xC 60. No drastic change of the ESR spectra is observed with the onset of superconductivity, leading to a conclusion that the observed dominant ESR signal originates from a non-superconducting phase.

  16. Pseudotenfold symmetry in pentane-solvated C60 and C70

    NASA Astrophysics Data System (ADS)

    Fleming, R. M.; Kortan, A. R.; Hessen, B.; Siegrist, T.; Thiel, F. A.; Marsh, P.; Haddon, R. C.; Tycko, R.; Dabbagh, G.; Kaplan, M. L.; Mujsce, A. M.

    1991-07-01

    Crystals of C60 or C70 cocrystallized with n-pentane grow as elongated, ten-sided columns. X-ray diffraction shows ordering of C60 or C70 molecules along the column and a remarkable tenfold symmetry normal to the column. The ratio of the x-ray-diffraction vectors of the two lowest-order diffraction spots is nearly equal to the ``golden ratio,'' τ. Despite these similarities with decagonal, quasicrystalline order, the diffraction indicates crystalline order with a twinned unit cell.

  17. [Stability of C60 nanoparticles in aquatic systems].

    PubMed

    Fang, Hua; Shen, Bing-Bing; Jing, Jie; Lu, Ji-Lai; Wang, Yuan

    2014-04-01

    The influences of storage time, pH, electrolytes and organic matters on the stability of two different suspensions of C60 nanoparticles were investigated. The results showed that the C60 nanoparticles prepared by solvent substitution (C60/son) were more stable than that prepared by prolonged stirring (C60/aq), and kept stable for a period of time. Higher pH enhanced the stability of C60 nanoparticles. The presence of electrolyte made a dramatic decrease in the surface zeta potential and an increase in the particle size. The aggregation process of C60 nanoparticles exhibited slow and rapid regions, which was found to be consistent with the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory of colloidal stability. The critical coagulation concentration (CCC) values of C60/son, obtained from the intersection of the interpolated lines through the slow and fast regions, were estimated as 321 mmol x L(-1) NaCl, 316 mmol x L(-1) KCl, 9.6 mmol x L(-1) MgCl2 and 6.7 mmol x L(-1) CaCl2. The CCC values of C60/aq were estimated as 295 mmol x L(-1) NaCl, 278 mmol x L(-1) KCl, 7.8 mmol x L(-1) MgCl2 and 5.9 mmol x L(-1) CaCl2, which were much higher than their concentrations in natural waters. The presence of humic acid enhanced the stability of C60 nanoparticles, which was attributable to steric repulsion. Therefore, C60 nanoparticles will keep relatively stable in typical aquatic environments. PMID:24946585

  18. Carbon fullerenes (C60s) can induce inflammatory responses in the lung of mice

    SciTech Connect

    Park, Eun-Jung; Kim, Hero; Kim, Younghun; Yi, Jongheop; Choi, Kyunghee; Park, Kwangsik

    2010-04-15

    Fullerenes (C60s) occur in the environment due to natural and anthropogenic sources such as volcanic eruptions, forest fires, and the combustion of carbon-based materials. Recently, production and application of engineered C60s have also rapidly increased in diverse industrial fields and biomedicine due to C60' unique physico-chemical properties, so toxicity assessment on environmental and human health is being evaluated as a valuable work. However, data related to the toxicity of C60s have not been abundant up to now. In this study, we studied the immunotoxic mechanism and change of gene expression caused by the instillation of C60s. As a result, C60s induced an increase in sub G1 and G1 arrest in BAL cells, an increase in pro-inflammatory cytokines such as IL-1, TNF-alpha, and IL-6, and an increase of Th1 cytokines such as IL-12 and IFN-r in BAL fluid. In addition, IgE reached the maximum at 1 day after treatment in both BAL fluid and the blood, and decreased in a time-dependent manner. Gene expression of the MHC class II (H2-Eb1) molecule was stronger than that of the MHC class I (H2-T23), and an increase in T cell distribution was also observed during the experiment period. Furthermore, cell infiltration and expression of tissue damage related genes in lung tissue were constantly observed during the experiment period. Based on this, C60s may induce inflammatory responses in the lung of mice.

  19. Fullerene C60 as a multifunctional system for drug and gene delivery

    NASA Astrophysics Data System (ADS)

    Montellano, Alejandro; da Ros, Tatiana; Bianco, Alberto; Prato, Maurizio

    2011-10-01

    The fullerene family, and especially C60, has delighted the scientific community during the last 25 years with perspective applications in a wide variety of fields, including the biological and the biomedical domains. Several biomedical uses have been explored using water-soluble C60-derivatives. However, the employment of fullerenes for drug delivery is still at an early stage of development. The design and synthesis of multifunctionalized and multimodal C60 systems able to cross the cell membranes and efficiently deliver active molecules is an attracting challenge that involves multidisciplinary strategies. Promising results have emerged in the last years, bringing fullerenes again to the front of interest. Herein, the state of the art of this emerging field is presented and illustrated with some of the most representative examples.

  20. Disclinations in C60 molecular layers on WO2/W (110 ) surfaces

    NASA Astrophysics Data System (ADS)

    Bozhko, S. I.; Taupin, V.; Lebyodkin, M.; Fressengeas, C.; Levchenko, E. A.; Radikan, K.; Lübben, O.; Semenov, V. N.; Shvets, I. V.

    2014-12-01

    A scanning tunneling microscopy study of a planar close-packed C60 hexagonal molecular layer on a WO2/W (110 ) substrate reveals the existence of C60 domains exhibiting two preferred orientations at an angle with an underlying periodic groove structure in the substrate. An analysis of the van der Waals interactions between substrate and layer retrieves the observed misorientations as those corresponding to minima in the interaction energy of the substrate-layer system. The misorientation between two C60 domains is accommodated in a tilt boundary by a linear array of molecular structural units identified as disclination dipoles, i.e., rotational defects in the hexagonal structure of the layer. A field theory of disclinations and dislocations is used to construct maps of the elastic energy, strains, curvatures, and stresses induced by the lattice defects over the layer. The predicted regions of high compression are found to overlap with those where the fullerene molecules do not undergo rotation.

  1. Experimental and theoretical determination of the magnetic susceptibility of C60 and C70

    NASA Astrophysics Data System (ADS)

    Haddon, R. C.; Schneemeyer, L. F.; Waszczak, J. V.; Glarum, S. H.; Tycko, R.; Dabbagh, G.; Kortan, A. R.; Muller, A. J.; Mujsce, A. M.; Rosseinsky, M. J.; Zahurak, S. M.; Makhija, A. V.; Thiel, F. A.; Raghavachari, K.; Cockayne, E.; Elser, V.

    1991-03-01

    THE magnetic susceptibility of C60 and the possibility of magnetic-field-induced π-electron ring currents in this carbon spheroid have been of interest since the initial experiments on carbon clusters1. If the molecule is regarded as a sphere with a radius of 3.5 Å, on which 60 electrons are free to move, the Pauling ring-current model predicts a ring-current diamagnetic susceptibility 41 times the π-electron ring-current magnetic susceptibility of benzene with the field normal to the plane of the six-membered ring2,3. London theory predicts, however, that the π-electron ring currents in C60 should be weakly paramagnetic or diamagnetic, depending on the relative bond strengths used in the calculation2,3. With the availability of macroscopic quantities of C60 (ref. 4), it is now possible to study experimentally the magnetic properties of the molecule. Here we report on such measurements. We find that the diamagnetism of C60 is small, a result that we attribute to excited-state paramagnetic contributions to the π-electron ring-current magnetic susceptibility. Thus C60 seems to be an aromatic molecule with a vanishingly small π-electron ring-current magnetic susceptibility. We have performed similar measurements on C70, which indicate an appreciable π-electron diamagnetism, consistent with theoretical calculations. We attribute the differences in magnetic properties of these two molecules to their different fractions of five-membered ring structures. The fullerenes may thus constitute a class of compounds of 'ambiguous' aromatic character, traditional measures of which will not provide an adequate classification.

  2. Axis-dependent magnetic behavior of C60 and C60(10+). consequences of spherical aromatic character.

    PubMed

    Muñoz-Castro, A

    2015-06-28

    The magnetic response of C60 has been studied and compared to its spherical aromatic counterpart C60(10+), focusing on the overall and local shielding tensors. A high axis dependence behavior at the outside region of the structure is characterized, unravelling a characteristic pattern of the local chemical shift anisotropy as a consequence of the spherical aromatic behavior. PMID:26022142

  3. Addition reaction of alkyl radical to C60 fullerene: Density functional theory study

    NASA Astrophysics Data System (ADS)

    Tachikawa, Hiroto; Kawabata, Hiroshi

    2016-02-01

    Functionalized fullerenes are known as a high-performance molecules. In this study, the alkyl-functionalized fullerenes (denoted by R-C60) have been investigated by means of the density functional theory (DFT) method to elucidate the effects of functionalization on the electronic states of fullerene. Also, the reaction mechanism of alkyl radicals with C60 was investigated. The methyl, ethyl, propyl, and butyl radicals (denoted by n = 1-4, where n means the number of carbon atoms in the alkyl radical) were examined as alkyl radicals. The DFT calculation showed that the alkyl radical binds to the carbon atom of C60 at the on-top site, and a strong C-C single bond is formed. The binding energies of alkyl radicals to C60 were distributed in the range of 31.8-35.1 kcal mol-1 at the CAM-B3LYP/6-311G(d,p) level. It was found that the activation barrier exists before alkyl addition, the barrier heights were calculated to be 2.1-2.8 kcal mol-1. The electronic states of R-C60 complexes were discussed on the basis of the theoretical results.

  4. Relative Photoionization Cross Sections of Super-Atom Molecular Orbitals (SAMOs) in C60.

    PubMed

    Bohl, Elvira; Sokół, Katarzyna P; Mignolet, Benoit; Thompson, James O F; Johansson, J Olof; Remacle, Francoise; Campbell, Eleanor E B

    2015-11-25

    The electronic structure and photoinduced dynamics of fullerenes, especially C60, is of great interest because these molecules are model systems for more complex molecules and nanomaterials. In this work we have used Rydberg Fingerprint Spectroscopy to determine the relative ionization intensities from excited SAMO (Rydberg-like) states in C60 as a function of laser wavelength. The relative ionization intensities are then compared to the ratio of the photoionization widths of the Rydberg-like states, computed in time-dependent density functional theory (TD-DFT). The agreement is remarkably good when the same photon order is required to energetically access the excited states. This illustrates the predictive potential of quantum chemistry for studying photoionization of large, complex molecules as well as confirming the assumption that is often made concerning the multiphoton excitation and rapid energy redistribution in the fullerenes. PMID:26551039

  5. Shock compression and equation of state of C60 fullerite

    NASA Astrophysics Data System (ADS)

    Milyavskiy, Vladimir; Khishchenko, Konstantin; Utkin, Alexander; Yakushev, Vladislav; Zhuk, Andrey; Fortov, Vladimir

    2007-06-01

    Recently, we have experimentally studied shock compressibility of C60 fullerite and sound velocity in shock-compressed fullerite [1]. The Hugoniot of C60 fullerite had a set of peculiarities. Appearance of a rather hard carbon phase was detected at shock pressure ˜ 9 GPa. We assume that it is a 2D-polymerized C60 phase. With increase of shock pressure, destruction of this phase and formation of a graphite-like carbon occurs. With further increase of shock pressure, the graphite- like carbon transforms to a diamond-like phase. If shock pressure is higher than ˜ 33 GPa, shock compressibility of C60 fullerite is determined by the thermodynamic properties of the diamond-like phase. The results of the shock-wave measurements were used for the description of thermodynamic properties of C60 fullerite and products of its transformations in a wide range of pressures and temperatures. A semiempirical equation of state for the simple cubic phase of C60 fullerite is proposed. The EOS we have developed for fullerite C60 provides a consistent representation of the available experimental data. The work was supported by RFBR. [1] Milyavskiy V.V., Utkin A.V., Zhuk A.Z., Yakushev V.V. and Fortov V.E. Diamond and Rel. Mat. 14 (2005) 1920.

  6. C60 fullerene soil sorption, biodegradation, and plant uptake.

    PubMed

    Avanasi, Raghavendhran; Jackson, William A; Sherwin, Brie; Mudge, Joseph F; Anderson, Todd A

    2014-01-01

    Assessments of potential exposure to fullerenes and their derivatives in the environment are important, given their increasing production and use. Our study focused on fate processes that determine the movement and bioavailability of fullerenes in soil. We evaluated the sorption, biodegradation, and plant uptake of C60 fullerene using (14)C-labeled C60 solutions in water produced by either solvent exchange with tetrahydrofuran or sonication/extended mixing in water. Organic carbon appeared to have an important influence on C60 soil sorption. The log Koc values for (14)C60 were equivalent for sandy loam and silt loam (3.55 log[mL/g]) but higher for loam (4.00 log[mL/g]), suggesting that other factors, such as pH, clay content and mineralogy, and cation exchange capacity, also influence C60 soil sorption. There was little (14)CO2 production in the silt loam or the sandy loam soil after 754 and 328 days, respectively, suggesting high resistance of C60 to mineralization in soil. Plant uptake was generally low (∼7%), with most of the uptaken (14)C accumulating in the roots (40-47%) and smaller amounts of accumulation in the tuber (22-23%), stem (12-16%), and leaves (18-22%). Our results indicate that C60 released to the environment will not be highly bioavailable but will likely persist in soil for extended periods. PMID:24521447

  7. High-T c superconductivity in potassium-doped fullerene, K xC 60, via coupled C 60 (pπ) cluster molecular orbitals and dynamic Jahn-Teller coupling

    NASA Astrophysics Data System (ADS)

    Johnson, K. H.; McHenry, M. E.; Clougherty, D. P.

    1991-11-01

    Recently observed superconductivity at 18 K in potassium-doped fullerene, K xC 60, may be due to Cooper pairing of partially occupied icosahedral C 60 cluster t 1u (pπ) molecular orbitals, induced by cooperative dynamic Jahn-Teller coupling of these orbitals to “soft-mode” vibrations of the C 60 molecules, leading to a BCS-like mechanism. Predicted are a nonvanishing isotope effect and Tc increasing to 30 K or more with optimization of doping, and significant effects with pressure.

  8. Molecular simulation of C 60 adsorption onto a TiO 2 rutile (1 1 0) surface

    NASA Astrophysics Data System (ADS)

    Carvalho, A. J. Palace; Ramalho, J. P. Prates

    2010-06-01

    A Monte Carlo molecular simulation study is presented on the adsorption and growth of C 60 films on the surface of the (1 1 0) face of rutile. Simulations are performed for a temperature of 600 K using atomistic models both for the fullerene molecules and the TiO 2 surface. It is found in this work that C 60 is adsorbed preferably in an ordered arrangement along the surface depressions over the exposed undercoordinated Ti cations. At low densities adsorption occurs preferably at alternate rows, with locations in consecutive rows being occupied appreciably only at higher C 60 densities. At low densities, the fullerene molecules tend to aggregate into islands in the surface plane. Additional layers of C 60 form only as the density increases, and do so before a monolayer is completed in all consecutive rows. Full monolayer capacity obtained at the highest densities is about 0.9 C 60 molecules per nm 2, but this is only achieved by completing the packing of molecules in interstices at a slightly upper level. The fraction of the molecules that lie closest to the surface only amounts to 0.6 molecules per nm 2.

  9. Crystallinity and properties of C60 nanotubes improved by annealing and alcohol-soaking

    NASA Astrophysics Data System (ADS)

    Naito, K.; Matsuishi, K.

    2009-04-01

    Well-uniformed C60 nanotubes were grown at -20 °C with irradiation of red light using C60-saturated pyridine solution and isopropyl alcohol by a liquid-liquid interfacial precipitation method without ultrasonic pulverization. We attempted to improve their crystallinity by two post-treatments; thermal annealing and alcohol-soaking. The crystallinity of as-grown and dried C60 nanotubes, which was poor due to the evaporation of solvent molecules from crystals in the drying process, was improved by annealing around 220 °C for 5 hours in vacuum. Dramatic improvement of crystallinity of as-grown samples was achieved by soaking into methanol and then drying in air. Raman, infrared and X-ray diffraction results suggest that the methanol-soaked samples exhibit a solvated tetragonal structure. The crystallinity improved by methanol-soaking did not degrade after removal of methanol molecules from samples by thermal annealing. Photo-polymerization of the structurally-improved C60 nanotubes was examined to investigate an effect of crystallinity on the polymerization kinetics.

  10. Dependence of the band structure of C-60 monolayers on molecularorientations and doping observed by angle resolved photoemission

    SciTech Connect

    Brouet, V.; Yang, W.L.; Zhou, X.J.; Hussain, Z.; Shen, Z.X.

    2008-01-17

    We present angle resolved photoemission studies of C60monolayers deposited on Ag surfaces. The electronic structure of thesemonolayers is derived from the partial filling of the narrow, 6-folddegenerated, C60 conduction band. By comparing the band structure in twomonolayers deposited, respectively, on Ag(111) and Ag(100), we show thatthe molecular degree of freedom, in this case the relative orientationsbetween C60 molecules, is essential to describe the band structure. Wefurther show that the evolution of the band as a function of doping doesnot follow a rigid band-filling picture. Phase separation is observedbetween a metallic and an insulating phase, which might be a result ofstrong correlations.

  11. Aggregation and Deposition of C60 in Aqueous Systems

    EPA Science Inventory

    The extremely low water solubility of many fullerenes precludes aqueous solution processing for engineering applications and minimizes the potential for fullerene environmental effects in aqueous environments. However, studies have shown that C60 fullerene can form stable colloi...

  12. Structure and photophysics in C 60-micellar solutions

    NASA Astrophysics Data System (ADS)

    Eastoe, Julian; Crooks, Esther R.; Beeby, Andrew; Heenan, Richard K.

    1995-11-01

    Routes to the preparation of monomeric and colloidal C 60 in micellar solutions of non-ionic surfactants are described. UV-visible spectra and small-angle neutron scattering provide clear evidence for these two different forms. The micelles serve to stabilise the excited triplet state 3C 60 and the lifetime τT is increased by a factor of 3 as compared to 3C 60 in toluene. Furthermore, with monomeric dispersions in the presence of the electron donor DABCO, the radical anion C 60- is formed, with an unusually long lifetime τA = 16 ms. This lifetime is approximately 270 times longer than for γ-cyclodextrin. stabilised systems.

  13. Energetics and structural stability of Cs3C60

    SciTech Connect

    Saito, Susumu; Umemoto, Koichiro; Louie, Steven G.; Cohen, MarvinL.

    2003-12-15

    Using the ab initio pseudo potential total-energy method and the density-functional theory, we study the energetics of face-centered-cubic Cs3C60 which is a material of great interest as a possible high transition-temperature superconductor. At the optimized lattice constant the volume per C60 is found to be smaller than the most stable hexagon-coordination A15 phase, while the total energy of the fcc phase is about 0.9 eV higher than the A15 phase. These results indicate that a low-temperature and high-pressure synthesis method might be a possible way to produce the fcc Cs3C60 phase. In addition, it is also found that the A15 Cs3C60 should show a phase transformation from a hexagon-coordination phase to a pentagon-coordination phase under hydrostatic pressure.

  14. Mechanical characterization of C60 whiskers by MEMS bend testing

    NASA Astrophysics Data System (ADS)

    Larsson, M. P.; Lucyszyn, S.

    2009-04-01

    Little has been published on the mechanical characteristics of C60 whiskers, due to the inherent difficulties in physically mounting such small test samples. Earlier reported results suggested Young's modulus values of 32 and 54 GPa, with 130 and 160 micron diameter C60 nanowhiskers, respectively, using compressive deformation techniques. In our work, an experimental bespoke silicon-based microelectromechanical system has been developed to extract an other value. 1th as been found, through parameter extraction techniques, that a Young's modulus of only ~ 2 GPa is obtained with a C60 whisker having a diameter of 4 microns. By including the previously published data points, there is now strong evidence to suggest an inverse proportionality relationship between the Young's modulus and the diameter of a C60 whisker.

  15. Paper Models for Fullerenes C60-C84.

    ERIC Educational Resources Information Center

    Beaton, John M.

    1995-01-01

    Describes a system to construct paper models of all 51 of the possible fullerene isomers from C60 through C84. Provides students, teachers, and specialists with an inexpensive mechanism to follow the literature interplay on fullerene structures. (JRH)

  16. Hemicarceplexes modify the solubility and reduction potentials of C60.

    PubMed

    Wong, Tzu-Huan; Chang, Jia-Cheng; Lai, Chien-Chen; Liu, Yi-Hung; Peng, Shie-Ming; Chiu, Sheng-Hsien

    2014-04-18

    A highly stable C60-incarcerated hemicarceplex, which retains its molecular integrity after heating at 523 K in air for at least 3 h, significantly increases the solubility of C60 in nonpolar solvents and increases the reduction potentials of the entrapped fullerene. Modification with [(η(5)-C5Me5)Ru(II)](+) dramatically increases the solubility of this hemicarceplex in polar, protic solvents (e.g., MeOH). PMID:24665822

  17. Rotation, translation, charge transfer, and electronic structure of C60 on Cu(111) surface

    NASA Astrophysics Data System (ADS)

    Wang, Lin-Lin; Cheng, Hai-Ping

    2004-01-01

    The energetics and electronic structure of a C60 monolayer on Cu(111) surfaces have been investigated thoroughly via large-scale first-principles density functional theory. The calculated adsorption site and orientation of the molecule, and the work function are in excellent agreement with experimental observations. We find that the translational motion of C60 across Cu-Cu bonds can be barrierless, while a 360°, on-site rotational motion is subject to a barrier of 0.3 eV. A close to 0.8e- charge transfer per molecule from the surface to the C60 monolayer is determined, which provides important insights into a number of experimental measurements. Our analysis also indicates that the transferred electrons are localized in a plane between the molecule and surface, and that the bands near the Fermi level are highly hybrid between the surface and the molecule, reflecting a strong metal-fullerene coupling. Furthermore, an analysis of the dipole moment clarifies the puzzling phenomenon regarding the work function.

  18. Tailorable acceptor C(60-n)B(n) and donor C(60-m)N(m) pairs for molecular electronics.

    PubMed

    Xie, Rui-Hua; Bryant, Garnett W; Zhao, Jijun; Smith, Vedene H; Di Carlo, Aldo; Pecchia, Alessandro

    2003-05-23

    Our first-principles calculations demonstrate that C(60-n)B(n) and C(60-m)N(m) can be engineered as the acceptors and donors, respectively, needed for molecular electronics by properly controlling the dopant number n and m in C60. We show that acceptor C48B12 and donor C48N12 are promising components for molecular rectifiers, carbon nanotube-based n-p-n (p-n-p) transistors, and p-n junctions. PMID:12785911

  19. Soil microbial response to photo-degraded C60 fullerenes.

    PubMed

    Berry, Timothy D; Clavijo, Andrea P; Zhao, Yingcan; Jafvert, Chad T; Turco, Ronald F; Filley, Timothy R

    2016-04-01

    Recent studies indicate that while unfunctionalized carbon nanomaterials (CNMs) exhibit very low decomposition rates in soils, even minor surface functionalization (e.g., as a result of photochemical weathering) may accelerate microbial decay. We present results from a C60 fullerene-soil incubation study designed to investigate the potential links between photochemical and microbial degradation of photo-irradiated C60. Irradiating aqueous (13)C-labeled C60 with solar-wavelength light resulted in a complex mixture of intermediate products with decreased aromaticity. Although addition of irradiated C60 to soil microcosms had little effect on net soil respiration, excess (13)C in the respired CO2 demonstrates that photo-irradiating C60 enhanced its degradation in soil, with ∼ 0.78% of 60 day photo-irradiated C60 mineralized. Community analysis by DGGE found that soil microbial community structure was altered and depended on the photo-treatment duration. These findings demonstrate how abiotic and biotic transformation processes can couple to influence degradation of CNMs in the natural environment. PMID:26774781

  20. Charge transfer and surface scattering at Cu-C60 planar interfaces

    NASA Astrophysics Data System (ADS)

    Hebard, A. F.; Ruel, R. R.; Eom, C. B.

    1996-11-01

    Thin-film planar structures of Cu and C60 have been sequentially deposited onto sapphire substrates in high vacuum and studied using in situ resistivity measurements during deposition together with ex situ atomic force microscopy characterization of surface topography. Two different regimes of behavior are identified. In the first of these, the thin-film limit in which the Cu is thin enough to be in the coalescence regime with an islanded morphology, the presence of an adjacent C60 monolayer, doped by charge transfer from the metal, creates a shunting path and a corresponding pronounced decrease in resistance. The sheet resistance of overlying doped monolayers is found to be ~8000 Ω, with a corresponding room-temperature resistivity that is a factor of 2 less than that of the three-dimensional alkali-metal-doped compounds A3C60 (A=K, Rb). The enhanced conductivity of an underlying monolayer of C60 is sufficient to reduce the critical thickness at which an overlying Cu film becomes conducting by almost a factor of 2 even though the roughness of such films is enhanced over that of Cu films deposited directly on the substrate. In the second regime of behavior, the continuous film limit in which the Cu is thick enough to have a size-effect resistivity proportional to the reciprocal of the film thickness, the presence of an adjacent C60 monolayer gives rise to an increase in resistance. Measurements on a number of samples with different thicknesses reveal that this resistance increase is best described by diffuse surface scattering. A scattering cross section of 5 AṦ resulting from a fit to this model represents the contact area under each C60 molecule.

  1. Extraterrestrial Helium (He@C60) Trapped in Fullerenes in the Sudbury Impact Structure

    NASA Technical Reports Server (NTRS)

    Becker, L.; Bada, J. L.; Poreda, R. J.; Bunch, T. E.

    1997-01-01

    Fullerenes (C60 and C70) have recently been identified in a shock-produced breccia (Onaping Formation) associated with the 1.85-Ga Sudbury Impact Crater. The presence of parts-per-million levels of fullerenes in this impact structure raises interesting questions about the processes that led to the formation of fullerenes and the potential for delivery of intact organic material to the Earth by a large bolide (e.g., asteroid or comet). Two possible scenarios for the presence of fullerenes in the Sudbury impact deposits are that (1) fullerenes are synthesized within the impact plume from the C contained in the bolide; or (2) fullerenes are already present in the bolide and survived the impact event. The correlation of C and trapped noble gas atoms in meteorites is well established. Primitive meteorites contain several trapped noble gas components that have anomalous isotopic compositions, some of which may have a presolar origin. Several C-bearing phases, including SiC, graphite, and diamond, have been recognized as carriers of trapped noble gases. It has also been suggested that fullerenes (C60 and C70) might be a carrier of noble gas components in carbonaceous chondrites. Recently, fullerenes have been detected in separate samples in the Allende meteorite. Carbon-60 is large enough to enclose the noble gases He, Ne, Ar, Kr, and Xe, but it is too small to contain diatomic gases such as N2 or triatomic gases such as CO2. Recent experimental work has demonstrated that noble gases of a specific isotopic composition can be introduced into synthetic fullerenes at high temperatures and pressures; these encapsulated gases can then be released by the breaking of one or more C bonds during step-heating under vacuum. These thermal-release patterns for He encapsulated within the C60 molecule (He@C60) are similar to the patterns for acid residues of carbonaceous chondrites, suggesting that fullerenes could be an additional carrier of trapped noble gases in acid residues of

  2. Elucidating the Significance of the ``Nano-Effect'' in Determining the Mobility of C60 Nanoparticles in Saturated Porous Media

    NASA Astrophysics Data System (ADS)

    Jia, Q.; Brant, J.

    2010-12-01

    Fullerenes are all carbon molecules that may exist in a variety of geometries, such as cages, cylinders, and planar sheets. Buckminsterfullerene (C60) is one type of fullerene that has received considerable interest from the scientific community for its use in commercial applications (bio-medical technologies, electronics, optics, and composites) and environmental implications (toxicity, mobility). Once released into the environment, the toxicity and bioavailability of C60 nanoparticles will be largely influenced by transport and retention processes in porous media. To date, many studies have investigated C60 mobility in saturated porous media, which has relevance to both groundwater protection and potable treatment by filtration methods. Previous research efforts have determined that the technique used for dispersing the C60 in water, chemistry of the dispersion solution (pH, ionic composition/strength), and Darcy velocity all affect C60 mobility. However, far less attention has been directed toward determining the impact of nanoparticle size. In other words, is there a nano-effect for C60, and if it exists to what extent does it alter C60 mobility in saturated porous media. The overall objective of this study was to explore to what extent the size of the C60 clusters (nC60) affects their mobility in saturated porous media in order to determine if the nano-effect does indeed exist for these systems. Nanoparticle mobility in two relatively well-characterized porous media, glass spheres and quartz sand, was assessed as a function of solution chemistry and Darcy velocity. The surface charge of the collector media was modified to elucidate the significance of charge interactions for nanoparticles. Preliminary results suggest that nC60 mobility increases as particle size decreases, supporting the belief that the nano-effect is indeed a real phenomenon.

  3. Alkylation of C60. Reaction between C60 anions and tert-butyl chloride and mass spectrometry analysis

    NASA Astrophysics Data System (ADS)

    Bourcier, S.; Chaurand, P.; Ciot, C.; Della-Negra, S.; Fabre, C.; Greugny, V.; Marx, L.; Rassat, A.; Rousseau, A.

    1996-11-01

    Alkylation of C60 in tetrahydrofuran with tert-butyl chloride and lithium gives a variety of products. Adducts of general formula C60Hn(t-Bu)qOx(thf)y (where t-Bu is the tert-butyl group and thf the tetrahydrofuryl group (C4H7O)) have been detected by mass spectrometry, with n <= 8, q + y <= 18 and x = 0, 1, 2 depending on experimental conditions. IR and NMR spectra of products confirm these assignments.

  4. A striking mobility improvement of C60 OFET by inserting diindenoperylene layer between C60 and SiO2 gate insulator

    NASA Astrophysics Data System (ADS)

    Yang, Jin-peng; Yonezawa, Keiichiro; Hinderhofer, Alexander; Bussolotti, Fabio; Kera, Satoshi; Ueno, Nobuo

    2014-09-01

    Gap states in organic semiconductors play a crucial role in determining Energy-Level Alignment and in many cases they act as charge trapping centers to result in serious lowering of charge mobility. Thus origin of gap states has gained increasing attention in order to realize higher mobility organic devises [1-4]. Bussolotti et al. have demonstrated recently that gap states in a pentacene thin film increase even by exposing the film to inert gas and confirmed that the gas exposure mediates structural defects in the film thus gap states [4]. The results have also indicated that preparation of highly-ordered organic thin film is necessary to improve the device performance, namely to decrease trapping states. To improve the ordering of molecule in the film, deposition of a template molecular underlayer is one of the simplest methods to increase the domain size of overlayer film and its crystallinity, and thus we expect improvement of the charge mobility [5]. Hinderhofer et al. reported recently that diindenoperylene (DIP; Figure 1a) could be used as a template layer to grow highly ordered and oriented C60 film with its (111) plane parallel to the SiO2 substrate [6]. Considering the hole mobility of DIP single crystal, which is quite low (~0.005 cm2 V-1S-1 at room temperature [7]), it is expected for the DIP template C60 thin film system that lower drain current would be achieved to improve the on/off ratios based on n type C60 transistor and its electron mobility (especially on the negative Vgs region, compared to PEN modified C60 transistors [8]).

  5. Heat of formation for C60 by means of the G4(MP2) thermochemical protocol through reactions in which C60 is broken down into corannulene and sumanene

    NASA Astrophysics Data System (ADS)

    Wan, Wenchao; Karton, Amir

    2016-01-01

    High-level heats of formation for C60 are obtained through the use of reactions in which C60 is broken down into its fundamental bowl-shaped aromatic fragments (corannulene and sumanene). The reaction enthalpies are obtained by means of the high-level G4(MP2) thermochemical protocol and reliable experimental (from the Active Thermochemical Tables, ATcT) or theoretical (from W1h theory) heats of formation are used for the molecules involved in these reactions. Our best theoretical estimate, ΔfH°298[C60(g)] = 2511.7 kJ mol-1, suggests that the experimental value adopted by the NIST thermochemical database (ΔfH°298[C60(g)] = 2560 ± 100 kJ mol-1) should be revised downwards.

  6. The Nature of the Noncovalent Interactions between Benzene and C60 Fullerene.

    PubMed

    Li, Ming-Ming; Wang, Yi-Bo; Zhang, Yu; Wang, Weizhou

    2016-07-21

    Noncovalent interactions between aromatic compounds and fullerenes have received considerable attention in various fields of science and technology. Employing benzene (C6H6) and C60 fullerene as model molecules, we theoretically explored in the present study the nature of this kind of noncovalent interaction. Our results clearly show that the π···π stacking configurations of the complex C6H6···C60 are more strongly bound than in the C-H···π analogues, and the C-H···π interactions in the C-H···π configurations of C6H6···C60 are not of the hydrogen bonds. According to symmetry adapted perturbation theory analyses, all of the configurations of C6H6···C60 are dominated by dispersion forces. The percentage of the dispersion components in the overall attractive interactions for the π···π stacking configurations is smaller than the percentage of the dispersion components in the overall attractive interactions for the C-H···π configurations, whereas the percentage of the electrostatic terms in the overall attractive interactions for the π···π stacking configurations is larger than the percentage of the electrostatic terms in the overall attractive interactions for the C-H···π configurations. This is distinctly different from the case of the benzene dimer. PMID:27366821

  7. Modulation of the photophysical properties of C60 by electronic confinement effect.

    PubMed

    Márquez, F; Sabater, M J

    2005-03-01

    This research work reports on the incorporation of fullerene C60 in diverse inorganic and organic matrixes and how these different environments induce changes on the photophysical properties of the molecule depending on the cavity dimensions of the host. Indeed the fluorescence emission band of C60 experiences a progressive bathochromic shift with respect to C60 in solution as the cavity dimensions of the host decrease in going from the mesoporous material MCM41 to UTD-1 and Na-Y zeolites. This experimental observation, which has been documentarily confirmed by theoretical predictions and recent experimental results, is a reflection of the confinement effect imposed by the host. However, the most striking result reported in this work is that the fluorescence range accessible to this occluded species can be extraordinarily extended by confinement inside the neutral cages of a "dendritic box". The ability of the dendritic shell to create a microenvironment, modifying the properties of its functional core, allows the emission bands of C60 incorporated into a dendrimer to be effectively red-shifted with respect to their emission in solution, and, contrarily to other confined spaces of considerable hardness such as zeolites or the high surface material MCM41, the magnitude of this shifting is maximum and can be modulated under appropriate experimental conditions. This phenomenon has an enormous relevance since it can be exploited in future technological applications. PMID:16833477

  8. Density functional calculation of superatomic molecular orbitals in C60: First truly converged results on a real grid mesh

    NASA Astrophysics Data System (ADS)

    Drake, Kyle; Bonacum, Jason; Zhang, Guo-Ping

    2014-03-01

    The molecular structure of Buckminster fullerene (C60) allows for electron delocalization in all of the pi-bonding electrons of the molecule. This coupled with the symmetry of the molecule allows for the formation of super-atomic molecular orbitals (SAMOs) similar to those observed in aluminum clusters. The SAMOs behave as if the molecule that they belong to is a single atom. We compute the eigenstates of C60 compulationally using density functional theory (DFT) and a grid mesh. Using larger radii also allows us to accurately describe SAMOs and test the convergence of our data. The results are interesting because for the first time, we can show the true converged super atomic orbitals in C60. Indiana State University SURE Program, Department of Energy, Indiana State University Department of Physics, and Indiana State University Center for Student Creativity and Research.

  9. ESR study of superconducting K-doped C 60 "polymer"

    NASA Astrophysics Data System (ADS)

    Kinoshita, N.; Grigoryan, L. S.; Kinoshita, T.; Tokumoto, M.

    1997-03-01

    ESR measurements of the superconducting K-doped C 60 "polymer" were carried out, in order to clarify the difference from ordinary K-doped C 60, i.e. monomer. Observed ESR spectrum was simulated by four Lorentzian lines. The temperature dependences of the ESR linewidth, g factor and spin susceptibility are obtained for each ESR line. At room temperature the linewidth and g factor of the broadest ESR absorption line are, about 400 G and 2.01, respectively. The linewidths for other lines are 150, 53 and 16 G with the common g factor of 2.000. The linewidths of the ESR spectrum of superconducting K-doped C 60 "polymer" are found to be much broader than those of monomer sample. Similar to monomer sample, two absorption lines with weakly temperature-dependent intensity were observed, one of which disappeared (150 G width) below the super-conducting transition temperature ( Tc = 15 K).

  10. C60 + in Diffuse Clouds: Laboratory and Astronomical Comparison

    NASA Astrophysics Data System (ADS)

    Campbell, E. K.; Holz, M.; Maier, J. P.

    2016-07-01

    The wavelengths of the strongest absorptions in the electronic spectrum of {{{C}}}60+ have been determined by experimental investigation into the perturbation caused by the helium in the laboratory spectra of {{{C}}}60+-{{{He}}}n(n=1{--}3). The extrapolation of these gives absorption bands of bare {{{C}}}60+ at 9348.4, 9365.2, 9427.8, 9577.0, and 9632.1 Å, with ±0.2 Å as the 2σ uncertainty. The laboratory data are compared with the complete set of astronomical observations reported in the literature. The spectral characteristics are found to be in agreement with five diffuse interstellar bands, for which the systematic uncertainties are larger than for the laboratory data.

  11. Radial vibrations of a sodium ion inside icosahedral C60

    NASA Technical Reports Server (NTRS)

    Ballester, J. L.; Dunlap, B. I.

    1992-01-01

    The very high symmetry of icosahedral C60 suggests that, as a first approximation, an atom trapped inside C60 would be subject to a potential that is radially symmetric about the center. All-electron local-density-functional calculations of the total energy of a sodium ion as a function of radial displacement from the center along the fivefold axis of C60 serve to refine such a radial potential. In particular, the calculations suggest studying potentials that have minima displaced from the center. An analytic functional form for a radial potential having a positive cusp at the origin is proposed, and the s-wave radial solutions of the corresponding Schroedinger equation are examined.

  12. A search for C60 in carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

    De Vries, M. S.; Reihs, K.; Wendt, H. R.; Golden, W. G.; Hunziker, H. E.; Fleming, R.; Peterson, E.; Chang, S.

    1993-01-01

    Analysis of interior samples of the Murchison meteorite by two routes yielded an upper limit of 2 ppb for its C60 content, as compared to parts per million levels for individual polycyclic aromatic hydrocarbons (PAHs ). Provided the samples contain an interstellar component, which is probable since Murchison hydrocarbons contain excess deuterium, this result argues against the ubiquitous presence of C60 in the interstellar medium. A possible explanation for the absence of C60 was found in experiments showing how PAHs replace fullerenes as stable end products when hydrogen is present during carbon condensation. As a secondary result we found high molecular weight PAHs in the Murchison and Allende meteorites. Coronene and its methyl derivatives are especially interesting since features in the coronene spectrum have been shown to match some of the unidentified interstellar infrared emission bands.

  13. Magnetic phases and relaxation effects in fullerite C60

    NASA Astrophysics Data System (ADS)

    Chigvinadze, J. G.; Buntar, V.; Ashimov, S. M.; Dolbin, A. V.

    2016-02-01

    A highly sensitive torsional vibration technique is used to study the magnetic properties of fullerite C60 (99.98%) at temperatures of 77-300 K in dynamic and static experiments. Vibrational energy absorption peaks associated with phase transitions and realignment of the magnetic structure of the fullerite are detected at T = 152, 195, 230, and 260 K. Relaxation magnetic processes in fullerite C60 at room temperature are studied. "Spontaneous" rotation of a motionless sample of fullerite freely suspended on an elastic filament is observed when external longitudinal or transverse magnetic fields are switched on. The direction of the "spontaneous" rotation changes with time. It is proposed that these phenomena are related to relaxation processes in the rotational subsystem of C60 molecular rotators, as well as to magnetic flux trapped in the fullerite and weakly damped eddy currents induced in the sample by the applied field.

  14. Charging C60 islands with the AFM tip.

    PubMed

    Hoff, Brice; Henry, Claude R; Barth, Clemens

    2016-01-01

    We show that electrons can be transferred on demand from an AFM tip into single bulk-like C60 islands, which are supported on the insulating NaCl(001) surface. We exemplify this by controlled charge-manipulation experiments conducted in ultrahigh vacuum by noncontact AFM (nc-AFM), electrostatic force microscopy (EFM) and Kelvin probe force microscopy (KPFM). KPFM shows a homogeneous contrast at the islands, which is a signature for an equal distribution of the electrons in the T1u band. The charge dissipates during half a day due to an interaction of the charged C60 islands with defects in the near surface region of NaCl. Our results open the perspective in photo-voltaics to study charge attachment, stability and charge exchange with the environment of any C60 bulk-like system. PMID:26617348

  15. Helium Droplets Doped with Sulfur and C60

    PubMed Central

    2014-01-01

    Clusters of sulfur are grown by passing superfluid helium nanodroplets through a pickup cell filled with sulfur vapor. In some experiments the droplets are codoped with C60. The doped droplets are collided with energetic electrons and the abundance distributions of positively and negatively charged cluster ions are recorded. We report, specifically, distributions of Sm+, Sm–, and C60Sm– containing up to 41 sulfur atoms. We also observe complexes of sulfur cluster anions with helium; distributions are presented for HenSm– with n ≤ 31 and m ≤ 3. The similarity between anionic and cationic C60Sm± spectra is in striking contrast to the large differences between spectra of Sm+ and Sm–. PMID:26045732

  16. Ionisation of C60: is it temperature dependent?

    NASA Astrophysics Data System (ADS)

    Baba, M. Sai; Narasimhan, T. S. Lakshmi; Balasubramanian, R.; Mathews, C. K.

    1994-01-01

    In a recent paper, Drewello [T. Drewello, W. Kratschmer, M. Fieber-Erdmann and A. Ding, Int. J. Mass Spectrom. Ion Processes, 124 (1993) R1] reported a temperature dependent ionisation cross section for the formation of C2+60 in their photoionisation dynamic studies on C60 using synchrotron radiation. To check this, the ratio of ion intensities of C2+60 to that of C60 was determined as a function of temperature of C60 samples using a Knudsen effusion mass spectrometer. Our results indicate the absence of any temperature dependence of cross section for the formation of C2+60 in the temperature range of measurement (600-800 K) using electron impact ionisation.

  17. The effect of glass transition in fullerite C60 on Ar impurity diffusion

    NASA Astrophysics Data System (ADS)

    Dolbin, A. V.; Esel'son, V. B.; Gavrilko, V. G.; Manzhelii, V. G.; Vinnikov, N. A.; Basnukaeva, R. M.

    2013-04-01

    The kinetics of sorption and subsequent desorption of argon gas by powdered fullerite C60 has been investigated in the temperature interval 58-290 K. The temperature dependence of the Ar diffusion coefficients in fullerite has been obtained using measured characteristic times of sorption. The diffusion coefficients for Ar decrease monotonically with decreasing temperature in the entire temperature range, which corresponds to the thermally activated diffusion of Ar atoms in fullerite. The glass transition in fullerite induces an order-of magnitude decrease in the activation energy of Ar diffusion in fullerite. This appears to be due to new paths that appeared as a result of the glass transition, in which the barriers separating the interstitial voids in the C60 lattice are significantly lower.

  18. Charging C60 islands with the AFM tip

    NASA Astrophysics Data System (ADS)

    Hoff, Brice; Henry, Claude R.; Barth, Clemens

    2015-12-01

    We show that electrons can be transferred on demand from an AFM tip into single bulk-like C60 islands, which are supported on the insulating NaCl(001) surface. We exemplify this by controlled charge-manipulation experiments conducted in ultrahigh vacuum by noncontact AFM (nc-AFM), electrostatic force microscopy (EFM) and Kelvin probe force microscopy (KPFM). KPFM shows a homogeneous contrast at the islands, which is a signature for an equal distribution of the electrons in the T1u band. The charge dissipates during half a day due to an interaction of the charged C60 islands with defects in the near surface region of NaCl. Our results open the perspective in photo-voltaics to study charge attachment, stability and charge exchange with the environment of any C60 bulk-like system.We show that electrons can be transferred on demand from an AFM tip into single bulk-like C60 islands, which are supported on the insulating NaCl(001) surface. We exemplify this by controlled charge-manipulation experiments conducted in ultrahigh vacuum by noncontact AFM (nc-AFM), electrostatic force microscopy (EFM) and Kelvin probe force microscopy (KPFM). KPFM shows a homogeneous contrast at the islands, which is a signature for an equal distribution of the electrons in the T1u band. The charge dissipates during half a day due to an interaction of the charged C60 islands with defects in the near surface region of NaCl. Our results open the perspective in photo-voltaics to study charge attachment, stability and charge exchange with the environment of any C60 bulk-like system. Electronic supplementary information (ESI) available. See DOI: 10.1039/C5NR04541J

  19. Anomalous enhancement in the infrared phonon intensity of a one-dimensional uneven peanut-shaped C60 polymer

    NASA Astrophysics Data System (ADS)

    Onoe, J.; Takashima, A.; Ono, S.; Shima, H.; Nishii, T.

    2012-05-01

    A one-dimensional (1D) uneven peanut-shaped C60 polymer formed from electron-beam (EB)-induced polymerization of C60 molecules showed an anomalous increase in two characteristic infrared (IR) peak intensities, which are respectively due to the radial and tangential motion of the 1D polymer, when compared to the IR peaks of pristine C60 films. This anomaly was analyzed on the basis of the vibrational van Hove singularity (VHS), using an extended thin-shell elastic model fully considering the effects of periodic radius modulation inherent to the 1D uneven peanut-shaped C60 polymer. We succeeded in explaining the enhancement in the tangential peak intensity by VHS, whereas the origin to cause that in the radial peak intensity is still unclear.

  20. Reaction Probability and Infrared Detection of the Primary Ozonide in Collisions of O3 with Surface-Bound C60.

    PubMed

    Davis, Erin Durke; Wagner, Alec; McEntee, Monica; Kaur, Manpreet; Troya, Diego; Morris, John R

    2012-11-01

    The kinetics and mechanism of reactions between gas-phase ozone and surface-bound C60 have been investigated by monitoring changes to reflection-absorption infrared spectra within a well-characterized film of C60 during exposure to a controlled flux of pure ozone. These ultrahigh vacuum studies provide direct infrared spectroscopic evidence for the formation and decomposition of a primary ozonide of C60. The spectral assignments of this highly unstable intermediate have been verified using electronic structure calculations. Theory and experiment revealed that C60 oxidized nearly exclusively via addition of ozone across the double bond that links two six-carbon-containing rings of the molecule. Following spectral characterization, the initial probability for ozone to react with the surface was found to be 5.8 ± 0.2 × 10(-4). Once formed, the ozonide quickly thermally decomposed to a variety of carbonyl-containing products. PMID:26296028

  1. Oxygen-Induced Degradation in C60-Based Organic Solar Cells: Relation Between Film Properties and Device Performance.

    PubMed

    Bastos, João P; Voroshazi, Eszter; Fron, Eduard; Brammertz, Guy; Vangerven, Tim; Van der Auweraer, Mark; Poortmans, Jef; Cheyns, David

    2016-04-20

    Fullerene-based molecules are the archetypical electron-accepting materials for organic photovoltaic devices. A detailed knowledge of the degradation mechanisms that occur in C60 layers will aid in the development of more stable organic solar cells. Here, the impact of storage in air on the optical and electrical properties of C60 is studied in thin films and in devices. Atmospheric exposure induces oxygen-trap states that are 0.19 eV below the LUMO of the fullerene C60. Moreover, oxygen causes a 4-fold decrease of the exciton lifetime in C60 layers, resulting in a 40% drop of short-circuit current from optimized planar heterojunction solar cells. The presence of oxygen-trap states increases the saturation current of the device, resulting in a 20% loss of open-circuit voltage. Design guidelines are outlined to improve air stability for fullerene-containing devices. PMID:27065475

  2. Structural and electronic properties of sodium-intercalated C60

    NASA Astrophysics Data System (ADS)

    Rosseinsky, M. J.; Murphy, D. W.; Fleming, R. M.; Tycko, R.; Ramirez, A. P.; Siegrist, T.; Dabbagh, G.; Barrett, S. E.

    1992-04-01

    The synthesis and initial characterization of bulk Na(x)C60 (x = 2-6) and mixed alkali phase Na2AC60 (where A is K, Rb, or Cs) are reported. All of these phases have intercalated fcc structures. The Na6C60 structure has a Na4 cluster centered on the octahedral site. The Na2AC60 compounds superconduct for the larger A cations, but a crossover to nonsuperconducting behavior occurs with decreasing cation size and correlates with a minimum in the unit cell volume.

  3. Resonant electron heating and molecular phonon cooling in single C60 junctions.

    PubMed

    Schulze, G; Franke, K J; Gagliardi, A; Romano, G; Lin, C S; Rosa, A L; Niehaus, T A; Frauenheim, Th; Di Carlo, A; Pecchia, A; Pascual, J I

    2008-04-01

    We study heating and heat dissipation of a single C(60) molecule in the junction of a scanning tunneling microscope by measuring the electron current required to thermally decompose the fullerene cage. The power for decomposition varies with electron energy and reflects the molecular resonance structure. When the scanning tunneling microscope tip contacts the fullerene the molecule can sustain much larger currents. Transport simulations explain these effects by molecular heating due to resonant electron-phonon coupling and molecular cooling by vibrational decay into the tip upon contact formation. PMID:18517981

  4. Electronic properties and phase transitions of RbC60 and CsC60: Investigation by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Tycko, R.; Dabbagh, G.; Murphy, D. W.; Zhu, Q.; Fischer, J. E.

    1993-09-01

    We report the results of 133Cs, 87Rb, and 13C NMR measurements on the alkali-metal fullerides CsC60 and RbC60. Measurements of NMR spectra and spin-lattice relaxation rates provide clear evidence for phase transitions near 300 K in both compounds, with substantial changes in their electronic properties at the phase transitions. The high-temperature phases are paramagnets, with an exchange coupling of roughly 2 cm-1 between electron spins that are localized primarily on C-60 ions. The 133Cs and 87Rb NMR frequency shifts and relaxation rates are determined by Fermi contact hyperfine couplings to the electron spins. The 13C relaxation rates are determined by dipolar hyperfine couplings. The electron-spin susceptibility is greatly reduced in the low-temperature phases

  5. Manufactured Nanomaterials (Fullerenes, C60) Induce Oxidative Stress in the Brain of Juvenile Largemouth Bass

    PubMed Central

    Oberdörster, Eva

    2004-01-01

    Although nanotechnology has vast potential in uses such as fuel cells, microreactors, drug delivery devices, and personal care products, it is prudent to determine possible toxicity of nanotechnology-derived products before widespread use. It is likely that nanomaterials can affect wildlife if they are accidentally released into the environment. The fullerenes are one type of manufactured nanoparticle that is being produced by tons each year, and initially uncoated fullerenes can be modified with biocompatible coatings. Fullerenes are lipophilic and localize into lipid-rich regions such as cell membranes in vitro, and they are redox active. Other nano-sized particles and soluble metals have been shown to selectively translocate into the brain via the olfactory bulb in mammals and fish. Fullerenes (C60) can form aqueous suspended colloids (nC60); the question arises of whether a redox-active, lipophilic molecule could cause oxidative damage in an aquatic species. The goal of this study was to investigate oxyradical-induced lipid and protein damage, as well as impacts on total glutathione (GSH) levels, in largemouth bass exposed to nC60. Significant lipid peroxidation was found in brains of largemouth bass after 48 hr of exposure to 0.5 ppm uncoated nC60. GSH was also marginally depleted in gills of fish, and nC60 increased water clarity, possibly due to bactericidal activity. This is the first study showing that uncoated fullerenes can cause oxidative damage and depletion of GSH in vivo in an aquatic species. Further research needs to be done to evaluate the potential toxicity of manufactured nanomaterials, especially with respect to translocation into the brain. PMID:15238277

  6. Hydrogen-Driven Cage Unzipping of C60 into Nano-Graphenes

    PubMed Central

    2014-01-01

    Annealing of C60 in hydrogen at temperatures above the stability limit of C–H bonds in C60Hx (500–550 °C) is found to result in direct collapse of the cage structure, evaporation of light hydrocarbons, and formation of solid mixture composed of larger hydrocarbons and few-layered graphene sheets. Only a minor part of this mixture is soluble; this was analyzed using matrix-assisted laser desorption/ionization MS, Fourier transform infrared (FTIR), and nuclear magnetic resonance spectroscopy and found to be a rather complex mixture of hydrocarbon molecules composed of at least tens of different compounds. The sequence of most abundant peaks observed in MS, which corresponds to C2H2 mass difference, suggests a stepwise breakup of the fullerene cage into progressively smaller molecular fragments edge-terminated by hydrogen. A simple model of hydrogen-driven C60 unzipping is proposed to explain the observed sequence of fragmentation products. The insoluble part of the product mixture consists of large planar polycyclic aromatic hydrocarbons, as evidenced by FTIR and Raman spectroscopy, and some larger sheets composed of few-layered graphene, as observed by transmission electron microscopy. Hydrogen annealing of C60 thin films showed a thickness-dependent results with reaction products significantly different for the thinnest films compared to bulk powders. Hydrogen annealing of C60 films with the thickness below 10 nm was found to result in formation of nanosized islands with Raman spectra very similar to the spectra of coronene oligomers and conductivity typical for graphene. PMID:24695911

  7. Spectroscopic and structural insights on molecular assembly consisting high potential zinc phthalocyanine photosensitizer attached to PyC60 through non-covalent interaction

    NASA Astrophysics Data System (ADS)

    Ray, Anamika; Santhosh, Kotni; Bhattacharya, Sumanta

    2015-01-01

    Efforts to improve the ease of self-assembly formation through non-covalent interaction has led to the development of zinc phthalocyanine (zinc-2,9,16,23-tetra-tert-butyl phthalocyanine, i.e., ZnPc) as a high potential photosensitizer molecule towards C60 pyrrolidine tris-acid ethyl ester (PyC60) in toluene and 1,2-dichlorobenzene (DCB). Steady state fluorescence experiment elicits efficient quenching of the fluorescence intensity of both H2- and ZnPc in presence of PyC60. The average value of binding constant for PyC60/H2-Pc and PyC60/ZnPc systems in toluene (DCB) are determined to be 9910 (13,460) and 12,710 (24,060) dm3 mol-1, respectively. Lifetime experiment yields ∼3 times larger magnitude of charge separated rate constant for the PyC60/ZnPc system compared to PyC60/H2-Pc in toluene. Photoinduced energy transfer between PyC60 and H2- (/ZnPc) has been evidenced with nanosecond laser photolysis method; transient absorption studies establish that energy transfer from TPyC60∗ to H2- and ZnPc occurs predominantly, as confirmed by the consecutive appearance of the triplet states of PyC60.

  8. Spectroscopic and structural insights on molecular assembly consisting high potential zinc phthalocyanine photosensitizer attached to PyC60 through non-covalent interaction.

    PubMed

    Ray, Anamika; Santhosh, Kotni; Bhattacharya, Sumanta

    2015-01-25

    Efforts to improve the ease of self-assembly formation through non-covalent interaction has led to the development of zinc phthalocyanine (zinc-2,9,16,23-tetra-tert-butyl phthalocyanine, i.e., ZnPc) as a high potential photosensitizer molecule towards C60 pyrrolidine tris-acid ethyl ester (PyC60) in toluene and 1,2-dichlorobenzene (DCB). Steady state fluorescence experiment elicits efficient quenching of the fluorescence intensity of both H2- and ZnPc in presence of PyC60. The average value of binding constant for PyC60/H2-Pc and PyC60/ZnPc systems in toluene (DCB) are determined to be 9910 (13,460) and 12,710 (24,060) dm(3) mol(-1), respectively. Lifetime experiment yields ∼3 times larger magnitude of charge separated rate constant for the PyC60/ZnPc system compared to PyC60/H2-Pc in toluene. Photoinduced energy transfer between PyC60 and H2- (/ZnPc) has been evidenced with nanosecond laser photolysis method; transient absorption studies establish that energy transfer from (T)PyC60(∗) to H2- and ZnPc occurs predominantly, as confirmed by the consecutive appearance of the triplet states of PyC60. PMID:25104284

  9. Exciton fission and charge generation via triplet excitons in pentacene/C60 bilayers.

    PubMed

    Rao, Akshay; Wilson, Mark W B; Hodgkiss, Justin M; Albert-Seifried, Sebastian; Bässler, Heinz; Friend, Richard H

    2010-09-15

    Organic photovoltaic devices are currently studied due to their potential suitability for flexible and large-area applications, though efficiencies are presently low. Here we study pentacene/C(60) bilayers using transient optical absorption spectroscopy; such structures exhibit anomalously high quantum efficiencies. We show that charge generation primarily occurs 2-10 ns after photoexcitation. This supports a model where charge is generated following the slow diffusion of triplet excitons to the heterojunction. These triplets are shown to be present from early times (<200 fs) and result from the fission of a spin-singlet exciton to form two spin-triplet excitons. These results elucidate exciton and charge generation dynamics in the pentacene/C(60) system and demonstrate that the tuning of the energetic levels of organic molecules to take advantages of singlet fission could lead to greatly enhanced photocurrent in future OPVs. PMID:20735067

  10. Thermopower of benzenedithiol and C60 molecular junctions with Ni and Au electrodes.

    PubMed

    Lee, See Kei; Ohto, Tatsuhiko; Yamada, Ryo; Tada, Hirokazu

    2014-09-10

    We have performed thermoelectric measurements of benzenedithiol (BDT) and C60 molecules with Ni and Au electrodes using a home-built scanning tunneling microscope. The thermopower of C60 was negative for both Ni and Au electrodes, indicating the transport of carriers through the lowest unoccupied molecular orbital in both cases, as was expected from the work functions. On the other hand, the Ni-BDT-Ni junctions exhibited a negative thermopower, whereas the Au-BDT-Au junctions exhibited a positive thermopower. First-principle calculations revealed that the negative thermopower of Ni-BDT-Ni junctions is due to the spin-split hybridized states generated by the highest occupied molecular orbital of BDT coupled with s- and d-states of the Ni electrode. PMID:25141337

  11. Optically enhanced charge transfer between C60 and single-wall carbon nanotubes in hybrid electronic devices.

    PubMed

    Allen, Christopher S; Liu, Guoquan; Chen, Yabin; Robertson, Alex W; He, Kuang; Porfyrakis, Kyriakos; Zhang, Jin; Briggs, G Andrew D; Warner, Jamie H

    2014-01-01

    In this article we probe the nature of electronic interactions between the components of hybrid C60-carbon nanotube structures. Utilizing an aromatic mediator we selectively attach C60 molecules to carbon nanotube field-effect transistor devices. Structural characterization via atomic force and transmission electron microscopy confirm the selectivity of this attachment. Charge transfer from the carbon nanotube to the C60 molecules is evidenced by a blue shift of the Raman G(+) peak position and increased threshold voltage of the transistor transfer characteristics. We estimate this charge transfer to increase the device density of holes per unit length by up to 0.85 nm(-1) and demonstrate further optically enhanced charge transfer which increases the hole density by an additional 0.16 nm(-1). PMID:24241690

  12. Synthesis and characterization of fullerene nanowhiskers by liquid-liquid interfacial precipitation: influence of C60 solubility.

    PubMed

    Sathish, Marappan; Miyazawa, Kun'ichi

    2012-01-01

    Fullerene nanowhiskers (FNWs) composed of C(60) fullerene molecules were prepared using the liquid-liquid interfacial precipitation (LLIP) method in the carbon-disulfide (CS(2)) and isopropyl alcohol (IPA) system. The electron microscopic images reveal the formation of non-tubular FNWs. The X-ray diffraction (XRD) pattern studies indicate the presence of fcc crystalline structure and unusual triclinic structure in the FNWs. The selected area electron diffraction pattern (SAED) analysis demonstrates the existence of triclinic and electron beam assisted fcc to tetragonal crystalline phase transformation. The formation of triclinic structure might be validated due to the partial polymerization of FNWs at C(60) saturated CS(2)-IPA interface. The high solubility of C(60) in CS(2) solvent system results in partial polymerization of FNWs. The polymerization of fullerene molecules in the FNWs has been further confirmed using Raman spectroscopy. PMID:22456616

  13. In situ x-ray photoelectron spectroscopic and density-functional studies of Si atoms adsorbed on a C60 film.

    PubMed

    Onoe, Jun; Nakao, Aiko; Hara, Toshiki

    2004-12-01

    The interaction between C(60) and Si atoms has been investigated for Si atoms adsorbed on a C(60) film using in situ x-ray photoelectron spectroscopy (XPS) and density-functional (DFT) calculations. Analysis of the Si 2p core peak identified three kinds of Si atoms adsorbed on the film: silicon suboxides (SiO(x)), bulk Si crystal, and silicon atoms bound to C(60). Based on the atomic percent ratio of silicon to carbon, we estimated that there was approximately one Si atom bound to each C(60) molecule. The Si 2p peak due to the Si-C(60) interaction demonstrated that a charge transfer from the Si atom to the C(60) molecule takes place at room temperature, which is much lower than the temperature of 670 K at which the charge transfer was observed for C(60) adsorbed on Si(001) and (111) clean surfaces [Sakamoto et al., Phys. Rev. B 60, 2579 (1999)]. The number of electrons transferred between the C(60) molecule and Si atom was estimated to be 0.59 based on XPS results, which is in good agreement with the DFT result of 0.63 for a C(60)Si with C(2v) symmetry used as a model cluster. Furthermore, the shift in binding energy of both the Si 2p and C 1s core peaks before and after Si-atom deposition was experimentally obtained to be +2.0 and -0.4 eV, respectively. The C(60)Si model cluster provides the shift of +2.13 eV for the Si 2p core peak and of -0.28 eV for the C 1s core peak, which are well corresponding to those experimental results. The covalency of the Si-C(60) interaction was also discussed in terms of Mulliken overlap population between them. PMID:15634092

  14. A detailed Auger electron spectroscopy study of the first stages of the growth of C60 thin films

    NASA Astrophysics Data System (ADS)

    Vidal, R. A.; Ferrón, J.

    2015-11-01

    In this work we take advantage of the large sensitivity and in-depth resolution of Auger electron spectroscopy (AES) to study in a detailed way the growth of C60 over different substrates, namely Cu(1 1 1), Si(1 0 0) and graphene. The ability of AES, as compared to more local probes like STM or AFM, to follow the process in a dynamic way, allows us to study the growth of C60 below and over one ML, including the change of C60 over either Si or Cu to the growth of C60 over a C60 film. We found that the growth always proceeds layer by layer. This result shows that differences in diffusion barriers are not as important as one may think following the idea of diffusion by a jumping mechanism. We propose that the sticking coefficient, governed by the adsorption energy, is responsible for the differences observed between Cu and Si. Our results also point to a different charge transfer among fullerene molecules and these surfaces. The same result is suggested in the case of C60 over graphene, but in this case our conclusion comes from the variable temperature experiments.

  15. STM imagery and density functional calculations of C60 fullerene adsorption on the 6H-SiC(0001)-3×3 surface

    NASA Astrophysics Data System (ADS)

    Ovramenko, T.; Spillebout, F.; Bocquet, F. C.; Mayne, A. J.; Dujardin, G.; Sonnet, Ph.; Stauffer, L.; Ksari, Y.; Themlin, J.-M.

    2013-04-01

    Scanning tunneling microscopy (STM) studies of the fullerene C60 molecule adsorbed on the silicon carbide SiC(0001)-3×3 surface, combined with density functional theory (DFT) calculations, show that chemisorption of individual C60 molecules occurs through the formation of one bond to one silicon adatom only in contrast to multiple bond formation on other semiconducting surfaces. We observe three stable adsorption sites with respect to the Si adatoms of the surface unit cell. Comprehensive DFT calculations give different adsorption energies for the three most abundant sites showing that van der Waals forces between the C60 molecule and the neighboring surface atoms need to be considered. The C60 molecules are observed to form small clusters even at low coverage indicating the presence of a mobile molecular precursor state and nonnegligible intermolecular interactions.

  16. Effect of Water Hydrogen Bonding on the Solvent-Mediated "Oscillatory" Repulsion of C60 Fullerenes in Water.

    PubMed

    Djikaev, Yuri S; Ruckenstein, Eli

    2015-05-01

    The solvent-mediated interaction of C60 fullerenes in liquid water is examined by using the combination of the probabilistic hydrogen bond model with the density functional theory. This combination allows one to take into account the effect of hydrogen bonding between water molecules on their interaction with fullerenes and to construct an approximation for the distribution of water molecules in the system, which provides an efficient foundation for studying hydrophobic phenomena. Our numerical evaluations predict the solvent-induced interaction of two C60 fullerenes in water at 293 K to have an oscillatory-repulsive character (previously observed in molecular dynamics simulations) only when the vicinal water-water hydrogen bonds are slightly weaker than bulk ones. Besides indicating the direction of the energetic alteration of water-water hydrogen bonds near C60 fullerenes, our model also suggests that the hydrogen bonding ability of water plays a defining role in the solvent-mediated C60-C60 repulsion. PMID:26263346

  17. The Environmental Fate of C60 Fullerenes: A Holistic Approach

    NASA Astrophysics Data System (ADS)

    Schreiner, K. M.; Filley, T. R.; Blanchette, R. A.; Jafvert, C.; Bolskar, R.

    2007-12-01

    The manufacture and use of carbon-based nanoparticles, for which C60 fullerenes can be considered a proxy, has grown exponentially in the past decade, and nanotechnology is now a multi-billion dollar industry, spanning disciplines such as cosmetics, biotechnology, and agriculture. Despite this, almost nothing is known of the fate of these compounds in the environment. Based upon the strong radical scavenging properties of many of these substances there are a variety of microbial and photochemical-mediated oxidative fates that will transform the physicochemical properties and control the residence time of these compounds in nature. It is essential that these fates, as well as the fates of the products of the degradation of carbon nanoparticles, are known. For instance, conversion of C60 fullerenes to hydroxylated or carboxylated analogs will shift the manner in which they partition between soils and sediments and water as well as how they interact with cell membranes. This paper combines our findings on the microbial activity of C60 fullerenes, one of the most common types of manufactured carbon nanoparticles, along with recent literature to develop potential chemical decay trajectories in oxidative environmental settings. We show what is known about the environmental fate of this type of nanomaterial and also areas where further research is needed.

  18. Photoionization and photofragmentation of the C60+ molecular ion

    NASA Astrophysics Data System (ADS)

    Baral, K. K.; Aryal, N. B.; Esteves-Macaluso, D. A.; Thomas, C. M.; Hellhund, J.; Lomsadze, R.; Kilcoyne, A. L. D.; Müller, A.; Schippers, S.; Phaneuf, R. A.

    2016-03-01

    Cross-section measurements are reported for single and double photoionization of C60+ ions in the photon energy range 18-150 eV accompanied by the loss of zero to seven pairs of carbon atoms, as well as for fragmentation without ionization resulting in loss of two to eight pairs of C atoms in the photon energy range 18-65 eV. Absolute measurements were performed by merging a beam of C60+ molecular ions with a beam of monochromatized synchrotron radiation. Product channels involving dissociation yielding smaller fullerene fragment ions account for nearly half of the total measured oscillator strength in this energy range. The sum of cross sections for the measured product channels is compared to a published calculation of the total photoabsorption cross section of neutral C60 based on time-dependent density-functional theory. This comparison and an accounting of oscillator strengths indicate that with the exception of C58+, the most important product channels resulting from photoabsorption were accounted for in the experiment. Threshold energies for the successive removal of carbon atom pairs accompanying photoionization are also determined from the measurements.

  19. Morphology Change of C60 Islands on Organic Crystals Observed by Atomic Force Microscopy.

    PubMed

    Freund, Sara; Hinaut, Antoine; Pawlak, Rémy; Liu, Shi-Xia; Decurtins, Silvio; Meyer, Ernst; Glatzel, Thilo

    2016-06-28

    Organic-organic heterojunctions are nowadays highly regarded materials for light-emitting diodes, field-effect transistors, and photovoltaic cells with the prospect of designing low-cost, flexible, and efficient electronic devices.1-3 However, the key parameter of optimized heterojunctions relies on the choice of the molecular compounds as well as on the morphology of the organic-organic interface,4 which thus requires fundamental studies. In this work, we investigated the deposition of C60 molecules at room temperature on an organic layer compound, the salt bis(benzylammonium)bis(oxalato)cupurate(II), by means of noncontact atomic force microscopy. Three-dimensional molecular islands of C60 having either triangular or hexagonal shapes are formed on the substrate following a "Volmer-Weber" type of growth. We demonstrate the dynamical reshaping of those C60 nanostructures under the local action of the AFM tip at room temperature. The dissipated energy is about 75 meV and can be interpreted as the activation energy required for this migration process. PMID:27219352

  20. Molecular Calculations of the Photoionization of Endohedral Atoms: Ar@C60

    NASA Astrophysics Data System (ADS)

    Ponzi, A.; Stener, M.; Decleva, P.; Manson, S. T.

    2014-05-01

    Endohedral fullerenes represent a particularly clean case of quantum confinement where the electronic properties of the guest atom or molecule are strongly modified by the encapsulating host.. Many theoretical studies, e.g, have been performed both on free C60 and endohedral systems, and the predicted confinement resonances have been confirmed by recent experiment. Most calculations have employed jellium models for the C60 moiety, allowing the treatment of electron response effects and interchannel coupling, while the few molecular calculations have been limited to a static description, either at the DFT or static-exchange level, giving, however, some conflicting evidence with interpretations based on jellium treatments. The development of large scale TDDFT codes allows full treatment of nonspherical and response effects, and this methods is applied to Ar@C60, to compare with results and assess the modifications brought about by the full inclusion of the ionic cores. It is found that molecular effects increase hybridization of the atomic orbitals with the cage and reduces the role of response effects, due to the stronger localization of the electron cloud.

  1. Determination of the sputtering yield of cholesterol using Arn(+) and C60(+(+)) cluster ions.

    PubMed

    Rakowska, P D; Seah, M P; Vorng, J-L; Havelund, R; Gilmore, I S

    2016-08-01

    The sputtering yield of cholesterol films on silicon wafers is measured using Arn(+) and C60(+(+)) ions in popular energy (E) and cluster size (n) ranges. It is shown that the C60(+(+)) ions form a surface layer that stabilizes the film so that a well-behaved profile is obtained. On the other hand, the Arn(+) gas clusters leave the material very clean but, at room temperature, the layer readily restructures into molecular bilayers, so that, although a useful measure may be made of the sputtering yield, the profiles become much more complex. This restructuring does not occur at room temperature normally but results from the actions of the beams in the sputtering process for profiling in secondary ion mass spectrometry. Better profiles may be made by reducing the sample temperature to -100 °C. This is likely to be necessary for many lower molecular weight materials (below 1000 Da) to avoid the movement of molecules. Measurements for cholesterol films on 37 nm of amiodarone on silicon are even better behaved and show the same sputtering yields at room temperature as those films directly on silicon at -100 °C. The yields for both C60(+(+)) and Arn(+) fit the Universal Equation to a standard deviation of 11%. PMID:27299934

  2. Effect of incorporated PVP/Ag nanoparticles on ZnPc/C60 organic solar cells.

    PubMed

    Heo, Ilsu; Kim, Jinhyun; Yim, Sanggyu

    2013-06-01

    Various sizes of PVP-capped Ag nanoparticles were incorporated in the PEDOT:PSS layer of ZnPc/C60-based small-molecule organic solar cells. The incorporated nanoparticles partially block the incident light, but this was offset by the scattering effect and consequent increase in path lengths through the active organic layers. As a result, the overall power conversion efficiency of the cell increased by approximately 15% when nanoparticles with an average diameter of 24 nm were used. PMID:23862493

  3. Mesoscale aggregation properties of C60 in toluene and chlorobenzene.

    PubMed

    Guo, Rong-Hao; Hua, Chi-Chung; Lin, Po-Chang; Wang, Ting-Yu; Chen, Show-An

    2016-07-20

    The mesoscale aggregation properties of C60 in two distinct aromatic solvents (toluene and chlorobenzene) and a practical range of concentrations (c = 1-2 and c = 1-5 mg mL(-1), respectively) were systematically explored by static/dynamic light scattering (SLS/DLS), small angle X-ray scattering (SAXS), depolarized dynamic light scattering (DDLS), and cryogenic transmission electron microscopy (cryo-TEM) analyses. The central observations were as follows: (1) aggregate species of sizes in the range of several hundred nanometers have been independently revealed by SLS, DLS, and DDLS analyses for both solvent systems. (2) DDLS and cryo-TEM measurements further revealed that while C60 clusters are notably anisotropic (rod-like) in chlorobenzene, they are basically isotropic (spherical) in toluene. (3) Detailed analyses of combined SLS and SAXS profiles suggested that varied, yet self-similar, solvent-induced aggregate units were responsible for the distinct (mesoscale) aggregation features noted above. (4) From a dynamic perspective, specially commissioned DLS measurements ubiquitously displayed two relaxation modes (fast and slow mode), with the second (slow) mode being q (wave vector) independent. While the fast mode in both solvent systems was basically diffusive by nature and leads to geometrical features in good agreement with the above static analyses, the slow mode was analyzed and tentatively suggested to reflect the effect of mutual confinement. (5) Micron-scale aggregate morphology of drop-cast thin films displays similar contrasting features for the two solvent media used. Overall, this study suggests that solvent-induced, nanoscale, aggregate units may be a promising factor to control a hierarchy of microscopic aggregation properties of C60 solutions and thin films. PMID:27376417

  4. Phase separation of co-evaporated ZnPc:C60 blend film for highly efficient organic photovoltaics

    NASA Astrophysics Data System (ADS)

    Zhou, Ying; Taima, Tetsuya; Miyadera, Tetsuhiko; Yamanari, Toshihiro; Kitamura, Michinori; Nakatsu, Kazuhiro; Yoshida, Yuji

    2012-06-01

    We demonstrate phase separation of co-evaporated zinc phthalocyanine (ZnPc) and fullerene (C60) for efficient organic photovoltaic cells. With introducing a poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) film and a crystalline copper iodide film on indium tin oxide, 20-nm-thick ZnPc film adopts a lying-down crystalline geometry with grain sizes of about 50 nm. This surface distributed with strong interaction areas and weak interaction areas enables the selective growth of ZnPc and C60 molecules during following co-evaporation, which not only results in a phase separation but also improve the crystalline growth of C60. This blend film greatly enhances the efficiencies in photocurrent generation and carrier transport, resulting in a high power conversion efficiency of 4.56% under 1 sun.

  5. Decay of C60 by delayed ionization and C2 emission: Experiment and statistical modeling of kinetic energy release

    NASA Astrophysics Data System (ADS)

    Lebeault, M.-A.; Baguenard, B.; Concina, B.; Calvo, F.; Climen, B.; Lépine, F.; Bordas, C.

    2012-08-01

    C60 molecules highly excited in the nanosecond regime decay following ionization and dissociation by emitting a series of carbon dimers, as well as other small fragments if excitation is strong enough. The fragmentation mass spectrum and kinetic energy release of all charged fragments obtained in these experiments are interpreted within the framework of the Weisskopf theory, using a realistic Monte Carlo procedure in which the rates of all relevant decay channels are modeled using Arrhenius expressions. Comparison between the measurements and the simulated spectra allows the distribution of deposited energy to be accurately estimated. The dependence of the fragment kinetic energies on the laser fluence, found in the simulation but not observed in the experimental results, indicates that the small fragments are not necessarily emitted from small fullerenes resulting from C60 by sequential decay. Rather, direct multifragmentation of C60 is invoked to interpret the observed patterns. The possible role of post-ionization of neutral emitted fragments is discussed.

  6. Structural influence on Raman scattering of a new C60 thin film prepared by AAO template with the method of pressure difference.

    PubMed

    Zhixun, Luo; Yan, Fang

    2006-01-01

    An anodic aluminum oxide (AAO) template is prepared by anodizing aluminum in oxalic acid solution. C60 crystals were grown, using the pressure difference method, in the pores of the template, representing a brushlike thin film layer with a honeycomb boundary structure in one side and nail arrays in the other side. Different Raman spectra of the C60 thin film from the both sides are presented, which indicate the different uniformly ordered structure character and the interface behavior of the C60 film on the surface with C60 crystals in the AAO nanopores. On the basis of energy and group theory, the strengthening of the Raman intensity and the broadening of Raman modes may imply that more transition spectral lines between vibration or rotation energy levels of C60 molecules were excited and detected. PMID:16827561

  7. Optically enhanced charge transfer between C60 and single-wall carbon nanotubes in hybrid electronic devices

    NASA Astrophysics Data System (ADS)

    Allen, Christopher S.; Liu, Guoquan; Chen, Yabin; Robertson, Alex W.; He, Kuang; Porfyrakis, Kyriakos; Zhang, Jin; Briggs, G. Andrew D.; Warner, Jamie H.

    2013-12-01

    In this article we probe the nature of electronic interactions between the components of hybrid C60-carbon nanotube structures. Utilizing an aromatic mediator we selectively attach C60 molecules to carbon nanotube field-effect transistor devices. Structural characterization via atomic force and transmission electron microscopy confirm the selectivity of this attachment. Charge transfer from the carbon nanotube to the C60 molecules is evidenced by a blue shift of the Raman G+ peak position and increased threshold voltage of the transistor transfer characteristics. We estimate this charge transfer to increase the device density of holes per unit length by up to 0.85 nm-1 and demonstrate further optically enhanced charge transfer which increases the hole density by an additional 0.16 nm-1.In this article we probe the nature of electronic interactions between the components of hybrid C60-carbon nanotube structures. Utilizing an aromatic mediator we selectively attach C60 molecules to carbon nanotube field-effect transistor devices. Structural characterization via atomic force and transmission electron microscopy confirm the selectivity of this attachment. Charge transfer from the carbon nanotube to the C60 molecules is evidenced by a blue shift of the Raman G+ peak position and increased threshold voltage of the transistor transfer characteristics. We estimate this charge transfer to increase the device density of holes per unit length by up to 0.85 nm-1 and demonstrate further optically enhanced charge transfer which increases the hole density by an additional 0.16 nm-1. Electronic supplementary information (ESI) available: AFM line scans of the substrate before and after functionalization; scheme for measuring amorphous carbon coverage from TEM images; diameter comparisons of ac-TEM image and simulation of C60 molecule; Raman spectra D peak comparison; optical response of transfer properties of pristine devices; comparison between swept and pulsed Vg measurements

  8. Continuum modeling investigation of gigahertz oscillators based on a C60 fullerene inside cyclic peptide nanotubes

    NASA Astrophysics Data System (ADS)

    Sadeghi, F.; Ansari, R.; Darvizeh, M.

    2016-02-01

    Research concerning the fabrication of nano-oscillators with operating frequency in the gigahertz (GHz) range has become a focal point in recent years. In this paper, a new type of GHz oscillators is introduced based on a C60 fullerene inside a cyclic peptide nanotube (CPN). To study the dynamic behavior of such nano-oscillators, using the continuum approximation in conjunction with the 6-12 Lennard-Jones (LJ) potential function, analytical expressions are derived to determine the van der Waals (vdW) potential energy and interaction force between the two interacting molecules. Employing Newton's second law, the equation of motion is solved numerically to arrive at the telescopic oscillatory motion of a C60 fullerene inside CPNs. It is shown that the fullerene molecule exhibits different kinds of oscillation inside peptide nanotubes which are sensitive to the system parameters. Furthermore, for the precise evaluation of the oscillation frequency, a novel semi-analytical expression is proposed based on the conservation of the mechanical energy principle. Numerical results are presented to comprehensively study the effects of the number of peptide units and initial conditions (initial separation distance and velocity) on the oscillatory behavior of C60 -CPN oscillators. It is found out that for peptide nanotubes comprised of one unit, the maximum achievable frequency is obtained when the inner core oscillates with respect to its preferred positions located outside the tube, while for other numbers of peptide units, such frequency is obtained when the inner core oscillates with respect to the preferred positions situated in the space between the two first or the two last units. It is further found out that four peptide units are sufficient to obtain the optimal frequency.

  9. Electronic and ionic conductivities in superionic Li4C60

    NASA Astrophysics Data System (ADS)

    Quintavalle, D.; Márkus, B. G.; Jánossy, A.; Simon, F.; Klupp, G.; Győri, M. A.; Kamarás, K.; Magnani, G.; Pontiroli, D.; Riccò, M.

    2016-05-01

    The 10 GHz microwave conductivity, σ (T ) and high field, 222 GHz electron spin resonance (HF-ESR) of Li4C60 fulleride is measured in a wide temperature range. We suggest that the majority of ESR active sites and at least some of the charge carriers for σ (T ) are electrons bound to a small concentration of surplus or vacancy ions in the polymer phase. Both σ (T ) and the ESR line shape depend on ionic motion. A change of the activation energy of σ (T ) at 125 K coincides with the onset of the ionic DC conductivity. The ESR line shape is determined mainly by Li ionic motion within octahedral voids below 150 K. At higher temperatures, fluctuations due to ionic diffusion change the environment of defects from axial to effectively isotropic on the ESR time scale. σ (T ) data up to 700 K through the depolymerization transition confirm that the monomeric phase of Li4C60 is a metal.

  10. Hot electron spin transport in C60 fullerene

    NASA Astrophysics Data System (ADS)

    Hueso, Luis Eduardo; Gobbi, Marco; Bedoya-Pinto, Amilcar; Golmar, Federico; Llopis, Roger; Casanova, Felix

    2012-02-01

    Carbon-based molecular materials are interesting for spin transport application mainly due to their small sources of spin relaxation [1]. However, spin coherence lengths reported in many molecular films do not exceed a few tens of nanometers [2]. In this work we will present results showing how hot spin-polarized electrons injected well above the Fermi level in C60 fullerene films travel coherently for hundreds of nanometers. We fabricated hot-electron vertical transistors, in which the current created across an Al/Al2O3 junction is polarized by a metallic Co/Cu/Py spin valve trilayer and subsequently injected in the molecular thin film. This geometry allows us to determine the energy level alignment at each interface between different materials. Moreover, the collector magnetocurrent excess 85%, even for C60 films thicknesses of 300 nm. We believe these results show the importance of hot spin-polarized electron injection and propagation in molecular materials. [1] V. Dediu, L.E. Hueso, I. Bergenti, C. Taliani, Nature Mater. 8, 707 (2009) [2] M. Gobbi, F. Golmar, R. Llopis, F. Casanova, L.E. Hueso, Adv. Mater. 23, 1609 (2011)

  11. Charge separated states and singlet oxygen generation of mono and bis adducts of C60 and C70

    NASA Astrophysics Data System (ADS)

    Dallas, Panagiotis; Rogers, Gregory; Reid, Ben; Taylor, Robert A.; Shinohara, Hisanori; Briggs, G. Andrew D.; Porfyrakis, Kyriakos

    2016-02-01

    We present a series of fullerene derivatives and a study on their photoluminescence properties, complete with their efficiency as singlet oxygen generation photosensitizers. We demonstrate the intramolecular charge transfer between pyrene donor and fullerene acceptor. The opposite effect in decay lifetime measurements is observed for the mono and bis adducts of C60 and C70 for the first time, indicating an interplay between charge-separation and locally excited states. A monoexponential decay was observed for the mono adduct of C60 and the bis adduct of C70, while a biexponential decay was observed for the bis adduct of C60 and the mono adduct of C70. The effect of these molecules as sensitizers of the singlet oxygen radical was tested using detailed 3D excitation photoluminescence maps. A quenching of the singlet oxygen for the C60-mono and C70-bis adducts was observed while a strong photosensitizing effect was observed for the C60-bis and C70-mono adducts.

  12. Methoxylation of Singly Bonded 1,4-1',4'-BnC60-C60Bn Dimer: Preferential Formation of 1,4-C60 Adduct with Sterically Less Demanding Addends and Stability Difference between 1,2- and 1,4-OMe(Bn)C60.

    PubMed

    He, Fa-Gui; Li, Zong-Jun; Gao, Xiang

    2016-08-01

    Methoxylation of the singly bonded 1,4-1',4'-BnC60-C60Bn dimer afforded 1,4-OMe(Bn)C60, a 1,4-C60 adduct with sterically less demanding addends, as the major adduct. The situation was different from that of direct functionalization of C60, where 1,2-OMe(Bn)C60 was obtained as the major product. The reaction was studied with in situ vis-NIR spectroscopy and computational calculations to obtain a better understanding of this unusual regioselectivity. The stability difference between 1,2- and 1,4-OMe(Bn)C60 was studied. PMID:27387300

  13. C60-dyad aggregates: Self-organized structures in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Guskova, O. A.; Varanasi, S. R.; Sommer, J.-U.

    2014-10-01

    Extensive full-atomistic molecular dynamics simulations are performed to study the self-organization of C60-fullerene dyad molecules in water, namely phenyl-C61-butyric acid methyl ester and fulleropyrrolidines, which have two elements of ordering, the hydrophobic fullerene cage and the hydrophilic/ionic group. While pristine fullerene or phenyl-C61-butyric acid methyl ester forms spherical droplets in order to minimize the surface tension, the amphiphilic nature of charged solute molecules leads to the formation of supramolecular assemblies having cylindrical shape driven by charge repulsion between the ionic groups located on the surface of the aggregates. We show that formation of non-spherical micelles is the geometrical consequence if the fullerene derivatives are considered as surfactants where the ionized groups are only hydrophilic unit. The agglomeration behavior of fullerenes is evaluated by determining sizes of the clusters, solvent accessible surface areas, and shape parameters. By changing the size of the counterions from chloride over iodide to perchlorate we find a thickening of the cylinder-like structures which can be explained by stronger condensation of larger ions and thus partial screening of the charge repulsion on the cluster surface. The reason for the size dependence of counterion condensation is the formation of a stronger hydration shell in case of small ions which in turn are repelled from the fullerene aggregates. Simulations are also in good agreement with the experimentally observed morphologies of decorated C60-nanoparticles.

  14. Symmetry-selected spin-split hybrid states in C60/ferromagnetic interfaces

    NASA Astrophysics Data System (ADS)

    Li, Dongzhe; Barreteau, Cyrille; Kawahara, Seiji Leo; Lagoute, Jérôme; Chacon, Cyril; Girard, Yann; Rousset, Sylvie; Repain, Vincent; Smogunov, Alexander

    2016-02-01

    The understanding of orbital hybridization and spin polarization at the organic-ferromagnetic interface is essential in the search for efficient hybrid spintronic devices. Here, using first-principles calculations, we report a systematic study of spin-split hybrid states of C60 deposited on various ferromagnetic surfaces: bcc-Cr(001), bcc-Fe(001), bcc-Co(001), fcc-Co(001), and hcp-Co(0001). We show that the adsorption geometry of the molecule with respect to the surface crystallographic orientation of the magnetic substrate as well as the strength of the interaction play a crucial role in the spin polarization of the hybrid orbitals. We find that a large spin polarization in vacuum above the buckyball can only be achieved if the molecule is adsorbed upon a bcc-(001) surface by its pentagonal ring. Therefore, bcc-Cr(001), bcc-Fe(001), and bcc-Co(001) are the optimal candidates. Spin-polarized scanning tunneling spectroscopy measurements on single C60 adsorbed on Cr(001) and Co/Pt(111) also confirm that the symmetry both of the substrate and of the molecular conformation has a strong influence on the induced spin polarization. Our finding may give valuable insights for further engineering of spin filtering devices through single molecular orbitals.

  15. Synthesis and characterization of highly photoresponsive fullerenyl dyads with a close chromophore antenna–C60 contact and effective photodynamic potential†

    PubMed Central

    Padmawar, Prashant A.; Rogers-Haley, Joy E.; So, Grace; Canteenwala, Taizoon; Thota, Sammaiah; Tan, Loon-Seng; Pritzker, Kenneth; Huang, Ying-Ying; Sharma, Sulbha K.; Kurup, Divya Balachandran; Hamblin, Michael R.; Wilson, Brian; Urbas, Augustine

    2010-01-01

    We report the synthesis of a new class of photoresponsive C60–DCE–diphenylaminofluorene nanostructures and their intramolecular photoinduced energy and electron transfer phenomena. Structural modification was made by chemical conversion of the keto group in C60(>DPAF-Cn) to a stronger electron-withdrawing 1,1-dicyanoethylenyl (DCE) unit leading to C60(>CPAF-Cn) with an increased electronic polarization of the molecule. The modification also led to a large bathochromic shift of the major band in visible spectrum giving measureable absorption up to 600 nm and extended the photoresponsive capability of C60–DCE–DPAF nanostructures to longer red wavelengths than C60(>DPAF-Cn). Accordingly, C60(>CPAF-Cn) may allow 2γ-PDT using a light wavelength of 1000–1200 nm for enhanced tissue penetration depth. Production efficiency of singlet oxygen by closely related C60(>DPAF-C2M) was found to be comparable with that of tetraphenylporphyrin photosensitizer. Remarkably, the 1O2 quantum yield of C60(>CPAF-C2M) was found to be nearly 6-fold higher than that of C60(>DPAF-C2M), demonstrating the large light-harvesting enhancement of the CPAF-C2M moiety and leading to more efficient triplet state generation of the C60> cage moiety. This led to highly effective killing of HeLa cells by C60(>CPAF-C2M) via photodynamic therapy (200 J cm−2 white light). We interpret the phenomena in terms of the contributions by the extended π-conjugation and stronger electron-withdrawing capability associated with the 1,1-dicyanoethylenyl group compared to that of the keto group. PMID:20890406

  16. Detection of C60 and C70 in a young planetary nebula.

    PubMed

    Cami, Jan; Bernard-Salas, Jeronimo; Peeters, Els; Malek, Sarah Elizabeth

    2010-09-01

    In recent decades, a number of molecules and diverse dust features have been identified by astronomical observations in various environments. Most of the dust that determines the physical and chemical characteristics of the interstellar medium is formed in the outflows of asymptotic giant branch stars and is further processed when these objects become planetary nebulae. We studied the environment of Tc 1, a peculiar planetary nebula whose infrared spectrum shows emission from cold and neutral C60 and C70. The two molecules amount to a few percent of the available cosmic carbon in this region. This finding indicates that if the conditions are right, fullerenes can and do form efficiently in space. PMID:20651118

  17. An ab-initio density functional theory investigation of fullerene/Zn-phthalocyanine (C60/ZnPc) interface with face-on orientation

    SciTech Connect

    Javaid, Saqib; Javed Akhtar, M.

    2015-07-28

    We have employed density functional theory to study the C60/ZnPc interface with face-on orientation, which has recently been tailored experimentally. For this purpose, adsorption of ZnPc on C60 has been studied, while taking into account different orientations of C60. Out of various adsorption sites investigated, 6:6 C-C bridge position in apex configuration of C60 has been found energetically the most favourable one with C60-ZnPc adsorption distance of ∼2.77 Å. The adsorption of ZnPc on C60 ensues both charge re-organization and charge transfer at the interface, resulting in the formation of interface dipole. Moreover, by comparing results with that of C60/CuPc interface, we show that the direction of interface dipole can be tuned by the change of the central atom of the phthalocyanine molecule. These results highlight the complexity of electronic interactions present at the C60/Phthalocyanine interface.

  18. An ab-initio density functional theory investigation of fullerene/Zn-phthalocyanine (C60/ZnPc) interface with face-on orientation

    NASA Astrophysics Data System (ADS)

    Javaid, Saqib; Javed Akhtar, M.

    2015-07-01

    We have employed density functional theory to study the C60/ZnPc interface with face-on orientation, which has recently been tailored experimentally. For this purpose, adsorption of ZnPc on C60 has been studied, while taking into account different orientations of C60. Out of various adsorption sites investigated, 6:6 C-C bridge position in apex configuration of C60 has been found energetically the most favourable one with C60-ZnPc adsorption distance of ˜2.77 Å. The adsorption of ZnPc on C60 ensues both charge re-organization and charge transfer at the interface, resulting in the formation of interface dipole. Moreover, by comparing results with that of C60/CuPc interface, we show that the direction of interface dipole can be tuned by the change of the central atom of the phthalocyanine molecule. These results highlight the complexity of electronic interactions present at the C60/Phthalocyanine interface.

  19. Preparation of C60-functionalized magnetic silica microspheres for the enrichment of low-concentration peptides and proteins for MALDI-TOF MS analysis.

    PubMed

    Chen, Hemei; Qi, Dawei; Deng, Chunhui; Yang, Penyuan; Zhang, Xiangmin

    2009-01-01

    In this work, for the first time, a novel C60-functionalized magnetic silica microsphere (designated C60-f-MS) was synthesized by radical polymerization of C60 molecules on the surface of magnetic silica microspheres. The resulting C60-f-MS microsphere has magnetite core and thin C60 modified silica shell, which endow them with useful magnetic responsivity and surface affinity toward low-concentration peptides and proteins. As a result of their excellent magnetic property, the synthesized C60-f-MS microspheres can be easily separated from sample solution without ultracentrifuge. The C60-f-MS microspheres were successfully applied to the enrichment of low-concentration peptides in tryptic protein digest and human urine via a MALDI-TOF MS analysis. Moreover, they were demonstrated to have enrichment efficiency for low-concentration proteins. Due to the novel materials maintaining excellent magnetic properties and admirable adsorption, the process of enrichment and desalting is very fast (only 5 min), convenient and efficient. As it has been demonstrated in the study, newly developed fullerene-derivatized magnetic silica materials are superior to those already available in the market. The facile and low-cost synthesis as well as the convenient and efficient enrichment process of the novel C60-f-MS microspheres makes it a promising candidate for isolation of low-concentration peptides and proteins even in complex biological samples such as serum, plasma, and urine or cell lysate. PMID:19086100

  20. UV-Vis, fluorescence and NMR spectroscopic investigations on inclusion properties of a designed tetrahomocalix[8]arene with fullerenes C 60 and C 70 in solution

    NASA Astrophysics Data System (ADS)

    Halder, Amal; Bhatt, Suchitra; Nayak, Sandip K.; Chattopadhyay, Subrata; Bhattacharya, Sumanta

    2011-12-01

    The present article reports the spectroscopic investigations on non-covalent interaction of fullerenes C 60 and C 70 with a macrocyclic receptor molecule, namely, 1,3,5,7-tetrahomo- p- tert-butylcalix[8]arene ( 1) in toluene. Jobs method of continuous variation reveals 1:1 stoichiometry for the fullerene complexes of 1. The most fascinating feature of the present study is that 1 binds selectively C 60 compared to C 70 as obtained from binding constant ( K) data of C 60- 1 ( KC60- 1) and C 70- 1 ( KC70- 1) complexes which are enumerated to be 265,000 dm 3 mol -1 and 63,430 dm 3 mol -1, respectively, and selectivity in binding ( KC60- 1/K C70- 1) is estimated to be 4.18 as obtained from UV-Vis study. Steady state fluorescence studies reveal quenching of fluorescence of 1 in presence of fullerenes and the K value of the C 60- 1 and C 70- 1 complexes are estimated to be 80,760 and 68,780 dm 3 mol -1, respectively, with selectivity in binding (K C60- 1/K C70- 1) ˜1.18. 1H NMR analysis provides very good support in favor of strong binding between C 60 and 1. The high value of K value for C 60- 1 complex indicates that 1 forms an inclusion complex with C 60.

  1. Solubility of C60 and PCBM in Organic Solvents.

    PubMed

    Wang, Chun I; Hua, Chi C

    2015-11-12

    The ability to correlate fullerene solubility with experimentally or computationally accessible parameters can significantly facilitate nanotechnology nowadays for a wide range of applications, while providing crucial insight into optimum design of future fullerene species. To date, there has been no single relationship that satisfactorily describes the existing data clearly manifesting the effects of solvent species, system temperature, and isomer. Using atomistic molecular dynamics simulations on two standard fullerene species, C60 and PCBM ([6,6]-phenyl-C61-butyric acid methyl ester), in a representative series of organic solvent media (i.e., chloroform, toluene, chlorobenzene, 1,3-dichlorobenzene, and 1,2-dichlorobenzene), we show that a single time constant characterizing the dynamic stability of a tiny (angstrom-sized) solvation shell encompassing the fullerene particle can be utilized to effectively capture the known trends of fullerene solubility as reported in the literature. The underlying physics differs substantially between the two fullerene species, however. Although C60 was previously shown to be dictated by a diffusion-limited aggregation mechanism, the side-chain-substituted PCBM is demonstrated herein to proceed with an analogous reaction-limited aggregation with the "reaction rate" set by the fullerene rotational diffusivity in the medium. The present results suggest that dynamic quantities-in contrast to the more often employed, static ones-may provide an excellent means to characterize the complex (entropic and enthalpic) interplay between fullerene species and the solvent medium, shed light on the factors determining the solvent quality of a nanoparticle solution, and, in particular, offer a practical pathway to foreseeing optimum fullerene design and fullerene-solvent interactions. PMID:26488132

  2. Preparation and characterisation of the C 60 charge transfer complex C 60-.[1,1',3,3'-tetramethyl-Δ 2,2'-bi(imidazolidine)] +.

    NASA Astrophysics Data System (ADS)

    Schilder, A.; Gotschy, B.; Seidl, A.; Gompper, R.

    1995-04-01

    Ferromagnetism in the C 60 charge transfer salt C 60-.[1,1',3,3'-tetramethyl-Δ 2,2'-bi(imidazolidine)] +. (C 60[TMBI]) with Curie temperatures Tc above 140 K and coercive forces Hc of about 1000 Oe were reported by Wang and Zhu (J. Phys. Chem. Solids 55 (1994) 437). This dramatic increase of Tc and Hc by a small variation of the counterion compared to the first C 60 ferromagnet C 60-.[tetrakis(dimethylamino)ethylene] +. (Allemand et al., Science 253 (1991) 301) triggered us to elucidate the charge transfer from TMBI to C 60 by absorption measurements in the VIS/NIR. We found that the reaction kinetics is much more complex than in C 60[TDAE]. Solid state investigations of C 60[TMBI] with EPR and microwave conductivity are in clear disagreement with the results published by Wang and Zhu. We found instead strong evidence that C 60[TMBI] is rather a diamagnetic C 60 CT complex with a lot of structural defects than a high temperature molecular ferromagnet.

  3. Precision printing and optical modeling of ultrathin SWCNT/C60 heterojunction solar cells.

    PubMed

    Guillot, Sarah L; Mistry, Kevin S; Avery, Azure D; Richard, Jonah; Dowgiallo, Anne-Marie; Ndione, Paul F; van de Lagemaat, Jao; Reese, Matthew O; Blackburn, Jeffrey L

    2015-04-21

    Semiconducting single-walled carbon nanotubes (s-SWCNTs) are promising candidates as the active layer in photovoltaics (PV), particularly for niche applications where high infrared absorbance and/or semi-transparent solar cells are desirable. Most current fabrication strategies for SWCNT PV devices suffer from relatively high surface roughness and lack nanometer-scale deposition precision, both of which may hamper the reproducible production of ultrathin devices. Additionally, detailed optical models of SWCNT PV devices are lacking, due in part to a lack of well-defined optical constants for high-purity s-SWCNT thin films. Here, we present an optical model that accurately reconstructs the shape and magnitude of spectrally resolved external quantum efficiencies for ultrathin (7,5) s-SWCNT/C60 solar cells that are deposited by ultrasonic spraying. The ultrasonic spraying technique enables thickness tuning of the s-SWCNT layer with nanometer-scale precision, and consistently produces devices with low s-SWCNT film average surface roughness (Rq of <5 nm). Our optical model, based entirely on measured optical constants of each layer within the device stack, enables quantitative predictions of thickness-dependent relative photocurrent contributions of SWCNTs and C60 and enables estimates of the exciton diffusion lengths within each layer. These results establish routes towards rational performance improvements and scalable fabrication processes for ultra-thin SWCNT-based solar cells. PMID:25790468

  4. COLLISION DYNAMICS OF X@C60(X = He, Ne, Ar) AT LOW ENERGIES

    NASA Astrophysics Data System (ADS)

    Zhao, Qiang; Zhang, Feng-Shou; Zhou, Hong-Yu

    2013-12-01

    In this paper, a semi-empirical molecular dynamics model is developed. The central collisions of C60 + C60 and X@C60 + X@C60 (X = He, Ne, Ar) at various incident energy are investigated within this model. The fullerene dimers like a "dumbbell" can be formed by a self-assembly of C60 fullerene and X@C60 (X = He, Ne) endohedral fullerenes, and the new fullerene structure like "peanut" can be formed by a self-assembly of Ar@C60. It is found that Ar atom plays a great role in the collision of Ar@C60 + Ar@C60 because of its size effect. The energy effect is found that various incident energies cannot change the final structure at low energies if they are below a certain energy.

  5. Review of the progress in model theoretical studies of e + A @C60 electron scattering

    NASA Astrophysics Data System (ADS)

    Dolmatov, V.; Amusia, M.; Chernysheva, L.

    2016-05-01

    A series of recent semi-empirical theoretical studies of electron scattering off endohedral atoms A@ C60 have identified interesting measurements as well as more rigorous calculations of e + A @C60 scattering to perform. This report provides the interested researchers with a review of the most significant findings of works on e + A @C60 scattering. First, we demonstrate features of e + A @C60 elastic scattering of slow electrons and low-frequency bremsstrahlung when both the atom A and the cage C60 are ``frozen''. Then, we ``unfrozen'' the atom A but keep the C60 cage ``frozen'' and demonstrate novel effects of dynamical polarization of the atom A under the ``frozen'' C60 confinement on e + A @C60 scattering. Finally, we demonstrate the combined effect of both the dynamical polarization of the encapsulated atom and the static polarization of C60 on the scattering process. Supported by the NSF grant PHY-1305085.

  6. Prediction of superalkali@C60 endofullerenes, their enhanced stability and interesting properties

    NASA Astrophysics Data System (ADS)

    Srivastava, Ambrish Kumar; Pandey, Sarvesh Kumar; Misra, Neeraj

    2016-07-01

    We introduce a new kind of endofullerenes by trapping superalkali (SA) species (the species possessing lower ionization energy than alkali metals) into C60. Employing density functional theory, we show that all SA@C60 are stable for SA = FLi2, OLi3 and NLi4. The DOS curves and HOMO-LUMO gaps of SA@C60 closely resemble those of Li@C60. The charge transfer from SA to C60 is larger than that of Li to C60 and consequently, the mean polarizability of SA@C60 and its depression increase. We, therefore, believe that SA@C60 endofullerenes might attract further attention for their possible applications, analogous to alkali metal doped C60.

  7. Generation of charge carriers in C60 films by 100-fs laser pulses with photon energies above and below the mobility edge

    SciTech Connect

    Chekalin, Sergei V; Yartsev, A P; Sundstroem, V

    2001-05-31

    Primary stages of photoinduced processes are studied in C60 films excited by 100-fs laser pulses at wavelengths of 645 and 367 nm, the fraction of excited molecules being no more than several percent. Probing in the broad spectral range from 400 to 1100 nm showed that both charged (cations and electrons) and neutral (excited molecules) components were produced upon irradiation by the laser pulse. For both excitation wavelengths, charge carriers were produced due to direct optical excitation rather than due to singlet-singlet annihilation. Anions were produced with a delay of 10{sup -13} - 10{sup -11} s through electron trapping by C60 molecules. (femtosecond technologies)

  8. Variation of excited-state dynamics in trifluoromethyl functionalized C60 fullerenes.

    PubMed

    Park, Jaehong; Ramirez, Jessica J; Clikeman, Tyler T; Larson, Bryon W; Boltalina, Olga V; Strauss, Steven H; Rumbles, Garry

    2016-08-17

    We report on electronically excited-state dynamics of three different trifluoromethyl C60 fullerenes (TMFs, C60(CF3)n: C60/4-1, C60/6-2, and C60/10-1, featuring four, six, and ten trifluoromethyl groups, respectively) using steady-state and time-resolved optical spectroscopy as well as ultrafast pump/probe transient absorption spectroscopy. C60/4-1 and C60/6-2 dissolved in toluene solvent show near-unity S1 → T1 intersystem crossing quantum yield (ΦISC), ca. 1 ns S1-state lifetimes, and microsecond-timescale T1-state lifetimes, which are typical of the fullerene class. On the other hand, C60/10-1 exhibits a dominant sub-nanosecond nonradiative S1 → S0 relaxation mechanism and negligible ΦISC, therefore decreasing the average excited-state lifetime (τavg) by about 5 orders of magnitude compared to that of C60/4-1 and C60/6-2 (τavg ≈ 17 μs and 54 μs for C60/4-1 and C60/6-2, respectively, whereas τavg ≈ 100 ps for C60/10-1). These excited-state characteristics of C60/4-1 and C60/6-2 are preserved in polymer matrix, suggesting that fullerene/polymer interactions do not modulate intrinsic photophysics of trifluoromethyl-substituted fullerenes. The contrasting excited-state study results of C60/4-1 and C60/6-2 to that of C60/10-1 infer that intrinsic optical properties and excited-state dynamics can be affected by the substitution on the fullerene. PMID:27485768

  9. A memory/adder model based on single C60 molecular transistors

    NASA Astrophysics Data System (ADS)

    Stadler, R.; Ami, S.; Forshaw, M.; Joachim, C.

    2001-09-01

    A recent proposal, in which 1-bit memory cells and simple logic gates such as NOT and NOR gates were based on C60 molecules in an electromechanical grid acting as transistors, is extended to larger architectures. In order to meet the requirements of standard digital circuit architectures, some modifications have to be made compared to the original model. For example, the number of transistors has to be increased from two to thirteen for a single NOR gate to guarantee balanced logical levels. In the scheme employed to achieve this in the current work, all two-input gates, namely OR, AND and XOR gates, can be easily constructed using the same concept. These gates are then used to design a 1-bit full-adder and a clocked D-latch, which are then combined with the earlier proposed 1-bit memory cell as the basic constituents of a memory/adder model. Clocked signal transmissions, corresponding to the read process of two 2-bit words from memory cells, their movement through registers and finally their addition and passing the output through another register, are simulated using the electrical circuit software SPICE. For the design of this memory/adder circuit, 464 single C60 transistors are used.

  10. Study of Flux Ratio of C60 to Ar Cluster Ion for Hard DLC Film deposition

    SciTech Connect

    Miyauchi, K.; Toyoda, N.; Kanda, K.; Matsui, S.; Kitagawa, T.; Yamada, I.

    2003-08-26

    To study the influence of the flux ratio of C60 molecule to Ar cluster ion on (diamond like carbon) DLC film characteristics, DLC films deposited under various flux ratios were characterized with Raman spectrometry and Near Edge X-ray Absorption Fine Structure (NEXAFS). From results of these measurements, hard DLC films were deposited when the flux ratio of C60 to Ar cluster ion was between 0.7 and 4. Furthermore the DLC film with constant sp2 content was obtained in the range of the ratio from 0.7 to 4, which contents are lower values than that of conventional films such as RF plasma. DLC films deposited under the ratio from 1 to 4 had hardness from 40 to 45GPa. It was shown that DLC films with stable properties of low sp2 content and high hardness were formed even when the fluxes were varied from 1 to 4 during deposition. It was indicated that this process was useful in the view of industrial application.