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Sample records for c-60 molecule adsorbed

  1. Spectroscopic observations of the displacement dynamics of physically adsorbed molecules-CO on C60

    NASA Astrophysics Data System (ADS)

    Yuan, Chunqing; Yates, John T.

    2016-10-01

    In this paper, we observed physically adsorbed CO molecules on C60 surface being displaced by impinging noble gas atoms (He, Ne, Ar, Kr), either through a dynamic displacement process or an exothermic replacement process, depending on their adsorption energies. This displacement mechanism could shift from one to the other depending on the surface coverage and temperature. Furthermore, rotational energy of the impinging molecules may also contribute to the dynamic displacement process by supplying additional energy.

  2. Effect of substrate thickness on ejection of phenylalanine molecules adsorbed on free-standing graphene bombarded by 10 keV C60

    NASA Astrophysics Data System (ADS)

    Golunski, M.; Verkhoturov, S. V.; Verkhoturov, D. S.; Schweikert, E. A.; Postawa, Z.

    2017-02-01

    Molecular dynamics computer simulations have been employed to investigate the effect of substrate thickness on the ejection mechanism of phenylalanine molecules deposited on free-standing graphene. The system is bombarded from the graphene side by 10 keV C60 projectiles at normal incidence and the ejected particles are collected both in transmission and reflection directions. It has been found that the ejection mechanism depends on the substrate thickness. At thin substrates mostly organic fragments are ejected by direct collisions between projectile atoms and adsorbed molecules. At thicker substrates interaction between deforming topmost graphene sheet and adsorbed molecules becomes more important. As this process is gentle and directionally correlated, it leads predominantly to ejection of intact molecules. The implications of the results to a novel analytical approach in Secondary Ion Mass Spectrometry based on ultrathin free-standing graphene substrates and a transmission geometry are discussed.

  3. Intramolecular features of individual C 60 molecules on Si(100) observed by STM

    NASA Astrophysics Data System (ADS)

    Yao, Xiaowei; Ruskell, Todd G.; Workman, Richard K.; Sarid, Dror; Chen, Dong

    1996-12-01

    Intramolecular features (IMF) of a variety of individual C 60 molecules adsorbed on an Si(100)-(2 × 1) surface have been imaged by scanning tunneling microscopy under ultrahigh vacuum conditions. Features of individual C 60 molecules clearly show the local density of states superimposed on their cage structure. Both physisorbed (pre-annealed) and chemisorbed (post-annealed) species have been imaged on the same surface, exhibiting characteristics that depend on their bonding nature. Intramolecular features of a physisorbed C 60 molecule and of two chemisorbed molecules are presented.

  4. The bonding nature of individual C60 molecules to Si(100) surfaces

    NASA Astrophysics Data System (ADS)

    Yao, X.; Workman, R. K.; Peterson, C. A.; Chen, D.; Sarid, D.

    It is demonstrated that bonding-dependent local density of states and energy levels of individual C60 molecules, adsorbed on Si(100)-(2×1) surfaces under ultra-high-vacuum conditions, can be obtained using scanning tunneling microscopy and spectroscopy. High-resolution images of individual C60 molecules, physisorbed (preannealed) and chemisorbed (postannealed) on different sites on the same sample, reveal clear intramolecular features superimposed on the molecules' cage structure that are consistent with their bonding nature. Spectroscopic measurements of individual C60 molecules chemisorbed at these sites yield energy levels that exhibit a transition of their electronic structure from that of a near-free adsorbate to that of SiC. The spectroscopic data corresponds to the observed changes in local density of states. These results demonstrate the power of scanning tunneling microscopy to determine the electronic structure and bonding characteristics of individual molecules.

  5. Poisson-distributed electron-transfer dynamics from single quantum dots to C60 molecules.

    PubMed

    Song, Nianhui; Zhu, Haiming; Jin, Shengye; Zhan, Wei; Lian, Tianquan

    2011-01-25

    Functional quantum dot (QD)-based nanostructures are often constructed through the self-assembly of QDs with binding partners (molecules or other nanoparticles), a process that leads to a statistical distribution of the number of binding partners. Using single QD fluorescence spectroscopy, we probe this distribution and its effect on the function (electron-transfer dynamics) in QD-C60 complexes. Ensemble-averaged transient absorption and fluorescence decay as well as single QD fluorescence decay measurements show that the QD exciton emission was quenched by electron transfer from the QD to C60 molecules and the electron-transfer rate increases with the C60-to-QD ratio. The electron-transfer rate of single QD-C60 complexes fluctuates with time and varies among different QDs. The standard deviation increases linearly with the average of electron-transfer rates of single QD-C60 complexes, and the distributions of both quantities obey Poisson statistics. The observed distributions of single QD-C60 complexes and ensemble-averaged fluorescence decay kinetics can be described by a model that assumes a Poisson distribution of the number of adsorbed C60 molecules per QD. Our findings suggest that, in self-assembled QD nanostructures, the statistical distribution of the number of adsorbed partners can dominate the distributions of the averages and standard deviation of their interfacial dynamical properties.

  6. Effective intermolecular potential and critical point for C60 molecule

    NASA Astrophysics Data System (ADS)

    Ramos, J. Eloy

    2017-07-01

    The approximate nonconformal (ANC) theory is applied to the C60 molecule. A new binary potential function is developed for C60, which has three parameters only and is obtained by averaging the site-site carbon interactions on the surface of two C60 molecules. It is shown that the C60 molecule follows, to a good approximation, the corresponding states principle with n-C8H18, n-C4F10 and n-C5F12. The critical point of C60 is estimated in two ways: first by applying the corresponding states principle under the framework of the ANC theory, and then by using previous computer simulations. The critical parameters obtained by applying the corresponding states principle, although very different from those reported in the literature, are consistent with the previous results of the ANC theory. It is shown that the Girifalco potential does not correspond to an average of the site-site carbon-carbon interaction.

  7. 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.

  8. Temperature effects of adsorption of C60 molecules on Si(111)-(7×7) surfaces

    NASA Astrophysics Data System (ADS)

    Chen, Dong; Sarid, Dror

    1994-03-01

    The adsorption of submonolayers C60 molecules on Si(111)-(7×7) surfaces, deposited at room temperature and then annealed to various elevated temperatures, is studied using scanning tunneling microscopy. For room temperature adsorption, the C60 molecules were observed to favor bonding to adatom bridge sites within a triangular half cell. After annealing to 600 °C, however, they were found to bond dominantly to adatom or restatom sites. The adsorbate-substrate interaction at room temperature is characterized by charge transfer from the substrate to the molecules. After the annealing process, however, the adsorbates bond covalently to the substrate. It is found that the desorption of the submonolayer adsorbates due to the annealing process is minimal. The surface diffusion of the adsorbates begins when annealing the sample to 700 °C, at which point the initial clustering of the adsorbates takes place. When annealing the sample to 850 °C, the C60 molecules decomposed on the sample surface and reacted with the Si atoms to form SiC islands.

  9. Atomic-scale mechanical properties of orientated C60 molecules revealed by noncontact atomic force microscopy.

    PubMed

    Pawlak, Rémy; Kawai, Shigeki; Fremy, Sweetlana; Glatzel, Thilo; Meyer, Ernst

    2011-08-23

    In this work, the mechanical properties of C(60) molecules adsorbed on Cu(111) are measured by tuning-fork-based noncontact atomic force microscopy (nc-AFM) and spectroscopy at cryogenic conditions. Site-specific tip-sample force variations are detected above the buckyball structure. Moreover, high-resolution images obtained by nc-AFM show the chemical structure of this molecule and describes unambiguously its orientations on the surface.

  10. Scanning tunneling microscopy and spectroscopy of individual C 60 molecules on Si(100)-(2 × 1) surfaces

    NASA Astrophysics Data System (ADS)

    Yao, Xiaowei; Ruskell, Todd G.; Workman, Richard K.; Sarid, Dror; Chen, Dong

    1996-11-01

    Individual C 60 molecules chemisorbed on Si(100)-(2 × 1) surfaces have been studied by scanning tunneling microscopy and spectroscopy. Chemisorption was realized by annealing the samples with room-temperature deposited adsorbates to 600°C. Spectroscopic results on individual adsorbates reveal a transition of their electronic structure from that of a near-free adsorbate to that of SiC, as the adsorbate-substrate interaction increases.

  11. Research on Electrostatic Propulsion Using C60 Molecules.

    DTIC Science & Technology

    2007-11-02

    fullerene extract containing C60 and C70 in a ratio of approximately 85% to 15%. The fullerene mix was Soxhlet extracted with toluene from soot. Pure C60...The objective of this program has been to determine properties of fullerenes relevant for electrostatic propulsion, to demonstrate ion extraction ...electrostatic propulsion, to demonstrate ion extraction from a discharge, and to assess the implications for fullerene ion thrusters. The experiments we

  12. Single-monolayer ordered phases of C60 molecules on Si(111)-(7×7) surfaces

    NASA Astrophysics Data System (ADS)

    Chen, Dong; Chen, Jian; Sarid, Dror

    1994-10-01

    We report on ultrahigh-vacuum scanning tunneling microscopy of submonolayers of C60 molecules adsorbed on a Si(111)-(7×7) surface and the statistics of their bonding sites. The images reveal that as the submonolayer coverage increases, the adsorbate-adsorbate interaction becomes larger than that of the adsorbate-substrate interaction. For a full monolayer coverage of adsorbates, the adsorbate-adsorbate interaction becomes strong enough and they form two ordered structural phases registered with those pinned on the substrate corner holes. This result is in contrast to a previous report [Phys. Rev. Lett. 70, 1850 (1993)] stating that several monolayers of adsorbates are required for the formation of the ordered structural phases.

  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

    2004-12-08

    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. (c) 2004 American Institute of Physics.

  14. 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.

  15. Interactions between two C60 molecules measured by scanning probe microscopies

    NASA Astrophysics Data System (ADS)

    Hauptmann, Nadine; González, César; Mohn, Fabian; Gross, Leo; Meyer, Gerhard; Berndt, Richard

    2015-11-01

    {{{C}}}60-functionalized tips are used to probe {{{C}}}60 molecules on Cu(111) with scanning tunneling and atomic force microscopy. Distinct and complex intramolecular contrasts are found. Maximal attractive forces are observed when for both molecules a [6,6] bond faces a hexagon of the other molecule. Density functional theory calculations including parameterized van der Waals interactions corroborate the observations.

  16. High resolution images of single C 60 molecules on gold (111) using scanning tunneling microscopy

    NASA Astrophysics Data System (ADS)

    Howells, Sam; Chen, Ting; Gallagher, Mark; Sarid, Dror; Lichtenberger, Dennis L.; Wright, Laura L.; Ray, Charles D.; Huffman, Donald R.; Lamb, Lowell D.

    1992-07-01

    The electronic interactions of fullerene molecules with metals, with other molecules, and with themselves are important to the chemical and conductive properties of these materials. We demonstrate high resolution scanning tunneling microscopy images of C 60 molecules condensed on epitaxial gold (111) films on mica, in which the C 60 molecules are isolated from each other. The C 60 molecules were locked in position to the gold substrate by an ordered layer of methyl isobutyl ketone. The images of the C 60 molecules exhibit intramolecular contrast indicating a significant electronic interaction with the gold substrate. Current versus voltage measurements show that both the C 60 and the thin film of methyl isobutyl ketone have conductances comparable to that of the gold substrate.

  17. 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.

  18. Formation of clusters composed of C60 molecules via self-assembly in critical fluids

    NASA Astrophysics Data System (ADS)

    Fukuda, Takahiro; Ishii, Koji; Kurosu, Shunji; Whitby, Raymond; Maekawa, Toru

    2007-04-01

    Fullerenes are promising candidates for intelligent, functional nanomaterials because of their unique mechanical, electronic and chemical properties. However, it is necessary to invent some efficient but relatively simple methods of producing structures composed of fullerenes for the development of nanomechatronic, nanoelectronic and biochemical devices and sensors. In this paper, we show that various structures such as straight fibres, networks formed by fibres, wide sheets and helical structures, which are composed of C60 molecules, are created by placing C60-crystals in critical ethane, carbon dioxide and xenon even though C60 molecules do not dissolve or disperse in the above fluids. It is supposed, judging by the intermolecular potentials between C60 and C60, between C60 and ethane, and between ethane and ethane, that C60-clusters grow with the assistance of solvent molecules, which are trapped between C60 molecules under critical conditions. This room-temperature self-assembly cluster growth process in critical fluids may open up a new methodology of forming structures built up with fullerenes without the need for any ultra-fine processing technologies.

  19. On the chemical behavior of C60 hosting H2O and other isoelectronic neutral molecules.

    PubMed

    Galano, Annia; Pérez-González, Adriana; del Olmo, Lourdes; Francisco-Marquez, Misaela; León-Carmona, Jorge Rafael

    2014-08-01

    The density functional theory (DFT) was used to investigate the chemical behavior of C60 hosting neutral guest molecules (NGM). The deformed atoms in molecules (DAM) allowed identifying the regions of electron density depletion and accumulation. The studied NGM are CH4, NH3, H2O, and HF. Based on dipole moment and polarizabilities analyses it is predicted that the NGM@C60 should be more soluble in polar solvents than C60. The deformations on the surface electron density of the fullerenes explain this finding, which might be relevant for further applications of these systems. It was found that the intrinsic reactivity of studied NGM@C60 is only moderately higher than that of C60. This trend is supported by the global reactivity indexes and the frontier orbitals analyses. The free radical scavenging activity of the studied systems, via single electron transfer, was found to be strongly dependent on the chemical nature of the reacting free radical. The presence of the studied NGM inside the C60 influences only to some extent the reactivity of C60 toward free radicals. The distortion of the electron density on the C60 cage, caused by the NGM, is directly related to the electron withdrawing capacity of the later.

  20. High-resolution imaging of C60 molecules using tuning-fork-based non-contact atomic force microscopy.

    PubMed

    Pawlak, R; Kawai, S; Fremy, S; Glatzel, T; Meyer, E

    2012-02-29

    Recent advances in non-contact atomic force microscopy (nc-AFM) have led to the possibility of achieving unprecedented resolution within molecular structures, accomplished by probing short-range repulsive interaction forces. Here we investigate C(60) molecules adsorbed on KBr(111) and Cu(111) by tuning-fork-based nc-AFM. First, measurements of C(60) deposited on KBr(001) were conducted in cryogenic conditions revealing highly resolved nc-AFM images of the self-assembly. Using constant-frequency shift mode as well as three-dimensional spectroscopic measurements, we observe that the relatively weak molecule-substrate interaction generally leads to the disruption of molecular assembled structures when the tip is probing the short-range force regime. This particular issue hindered us in resolving the chemical structure of this molecule on the KBr surface. To obtain a better anchoring of C(60) molecules, nc-AFM measurements were performed on Cu(111). Sub-molecular resolutions within the molecules was achieved which allowed a direct and unambiguous visualization of their orientations on the supporting substrate. Furthermore, three-dimensional spectroscopic measurements of simultaneous force and current have been performed above the single molecules giving information of the C(60) molecular orientation as well as its local conductivity. We further discuss the different imaging modes in nc-AFM such as constant-frequency shift nc-AFM, constant-height nc-AFM and constant-current nc-AFM as well as three-dimensional spectroscopic measurement (3D-DFS) employed to achieve such resolution at the sub-molecular scale.

  1. Spectromicroscopy of C60 and azafullerene C59N: Identifying surface adsorbed water.

    PubMed

    Erbahar, Dogan; Susi, Toma; Rocquefelte, Xavier; Bittencourt, Carla; Scardamaglia, Mattia; Blaha, Peter; Guttmann, Peter; Rotas, Georgios; Tagmatarchis, Nikos; Zhu, Xiaohui; Hitchcock, Adam P; Ewels, Chris P

    2016-10-17

    C60 fullerene crystals may serve as important catalysts for interstellar organic chemistry. To explore this possibility, the electronic structures of free-standing powders of C60 and (C59N)2 azafullerenes are characterized using X-ray microscopy with near-edge X-ray adsorption fine structure (NEXAFS) spectroscopy, closely coupled with density functional theory (DFT) calculations. This is supported with X-ray photoelectron spectroscopy (XPS) measurements and associated core-level shift DFT calculations. We compare the oxygen 1s spectra from oxygen impurities in C60 and C59N, and calculate a range of possible oxidized and hydroxylated structures and associated formation barriers. These results allow us to propose a model for the oxygen present in these samples, notably the importance of water surface adsorption and possible ice formation. Water adsorption on C60 crystal surfaces may prove important for astrobiological studies of interstellar amino acid formation.

  2. Spectromicroscopy of C60 and azafullerene C59N: Identifying surface adsorbed water

    PubMed Central

    Erbahar, Dogan; Susi, Toma; Rocquefelte, Xavier; Bittencourt, Carla; Scardamaglia, Mattia; Blaha, Peter; Guttmann, Peter; Rotas, Georgios; Tagmatarchis, Nikos; Zhu, Xiaohui; Hitchcock, Adam P.; Ewels, Chris P.

    2016-01-01

    C60 fullerene crystals may serve as important catalysts for interstellar organic chemistry. To explore this possibility, the electronic structures of free-standing powders of C60 and (C59N)2 azafullerenes are characterized using X-ray microscopy with near-edge X-ray adsorption fine structure (NEXAFS) spectroscopy, closely coupled with density functional theory (DFT) calculations. This is supported with X-ray photoelectron spectroscopy (XPS) measurements and associated core-level shift DFT calculations. We compare the oxygen 1s spectra from oxygen impurities in C60 and C59N, and calculate a range of possible oxidized and hydroxylated structures and associated formation barriers. These results allow us to propose a model for the oxygen present in these samples, notably the importance of water surface adsorption and possible ice formation. Water adsorption on C60 crystal surfaces may prove important for astrobiological studies of interstellar amino acid formation. PMID:27748425

  3. Spectromicroscopy of C60 and azafullerene C59N: Identifying surface adsorbed water

    NASA Astrophysics Data System (ADS)

    Erbahar, Dogan; Susi, Toma; Rocquefelte, Xavier; Bittencourt, Carla; Scardamaglia, Mattia; Blaha, Peter; Guttmann, Peter; Rotas, Georgios; Tagmatarchis, Nikos; Zhu, Xiaohui; Hitchcock, Adam P.; Ewels, Chris P.

    2016-10-01

    C60 fullerene crystals may serve as important catalysts for interstellar organic chemistry. To explore this possibility, the electronic structures of free-standing powders of C60 and (C59N)2 azafullerenes are characterized using X-ray microscopy with near-edge X-ray adsorption fine structure (NEXAFS) spectroscopy, closely coupled with density functional theory (DFT) calculations. This is supported with X-ray photoelectron spectroscopy (XPS) measurements and associated core-level shift DFT calculations. We compare the oxygen 1s spectra from oxygen impurities in C60 and C59N, and calculate a range of possible oxidized and hydroxylated structures and associated formation barriers. These results allow us to propose a model for the oxygen present in these samples, notably the importance of water surface adsorption and possible ice formation. Water adsorption on C60 crystal surfaces may prove important for astrobiological studies of interstellar amino acid formation.

  4. Caging effects in the low-temperature rotational spectra of endohedral diatomic molecules at C60 fullerene

    NASA Astrophysics Data System (ADS)

    Hernández-Rojas, J.; Bretón, J.; Gomez Llorente, J. M.

    1996-04-01

    Caging effects in the low-temperature (T=50 K) rotational spectra of CO@C60, LiF@C60, and LiH@C60 are investigated by first deriving an effective Hamiltonian to describe the coupled rotation of both, cage and confined molecule. Our results prove the close connection between the degree of anisotropy of the molecule-cage interaction and the features in the rotational spectra. If the anisotropy is weak, as in CO@C60, the spectra are dominated by the free rotation of the confined molecule. The stronger anisotropy in LiF@C60 and LiH@C60 produces more complex spectra dominated by librational motions and hindered rotations. The cage rotation plays a fundamental role in the spectral features, enhancing the CO free rotation in CO@C60, and broadening the librational bands in LiF@C60 and LiH@C60.

  5. Interceptor effect of C60 fullerene on the in vitro action of aromatic drug molecules.

    PubMed

    Skamrova, Galyna B; Laponogov, Ivan; Buchelnikov, Anatoly S; Shckorbatov, Yuriy G; Prylutska, Svitlana V; Ritter, Uwe; Prylutskyy, Yuriy I; Evstigneev, Maxim P

    2014-07-01

    C60 fullerenes are spherical molecules composed purely of carbon atoms. They inspire a particularly strong scientific interest because of their specific physico-chemical properties and potential medical and nanotechnological applications. In this work we are focusing on studying the influence of the pristine C60 fullerene on biological activity of some aromatic drug molecules in human buccal epithelial cells. Assessment of the heterochromatin structure in the cell nucleus as well as the barrier function of the cell membrane was performed. The methods of cell microelectrophoresis and atomic force microscopy were also applied. A concentration-dependent restoration of the functional activity of the cellular nucleus after exposure to DNA-binding drugs (doxorubicin, proflavine and ethidium bromide) has been observed in human buccal epithelial cells upon addition of C60 fullerene at a concentration of ~10(-5 )M. The results were shown to follow the framework of interceptor/protector action theory, assuming that non-covalent complexation between C60 fullerene and the drugs (i.e., hetero-association) is the major process responsible for the observed biological effects. An independent confirmation of this hypothesis was obtained via investigation of the cellular response of buccal epithelium to the coadministration of the aromatic drugs and caffeine, and it is based on the well-established role of hetero-association in drug-caffeine systems. The results indicate that C60 fullerene may reverse the effects caused by the aromatic drugs, thereby pointing out the potential possibility of the use of aromatic drugs in combination with C60 fullerene for regulation of their medico-biological action.

  6. Determination of the equilibrium constant of C60 fullerene binding with drug molecules.

    PubMed

    Mosunov, Andrei A; Pashkova, Irina S; Sidorova, Maria; Pronozin, Artem; Lantushenko, Anastasia O; Prylutskyy, Yuriy I; Parkinson, John A; Evstigneev, Maxim P

    2017-03-01

    We report a new analytical method that allows the determination of the magnitude of the equilibrium constant of complexation, Kh, of small molecules to C60 fullerene in aqueous solution. The developed method is based on the up-scaled model of C60 fullerene-ligand complexation and contains the full set of equations needed to fit titration datasets arising from different experimental methods (UV-Vis spectroscopy, (1)H NMR spectroscopy, diffusion ordered NMR spectroscopy, DLS). The up-scaled model takes into consideration the specificity of C60 fullerene aggregation in aqueous solution and allows the highly dispersed nature of C60 fullerene cluster distribution to be accounted for. It also takes into consideration the complexity of fullerene-ligand dynamic equilibrium in solution, formed by various types of self- and hetero-complexes. These features make the suggested method superior to standard Langmuir-type analysis, the approach used to date for obtaining quantitative information on ligand binding with different nanoparticles.

  7. Thiol-based molecular overlayers adsorbed on C60: role of the end-group and charge state on the stability of the complexes.

    PubMed

    Chavira-Quintero, R; Guirado-López, R A

    2013-11-07

    We present pseudo-potential density functional theory calculations dedicated to analyze the stability and electronic properties of thiol-based molecular overlayers adsorbed on C60. We consider short molecules having a S atom as a headgroup, alkyl chains containing one to three C atoms, and a CH3 species as a terminal group. The thiol molecules are bonded to the carbon surface (through the S atom) with adsorption energies that vary in the range of ~1-2 eV and with S-C bond lengths of ~1.8 Å. For neutral C60(SCH3)n complexes, low energy atomic configurations are obtained when the thiol groups are distributed on the surface forming small molecular domains (e.g., pairs, trimers, or tetramer configurations of neighboring thiol molecules). In contrast, less stable random distributions are defined by orientationally disordered overlayers with highly distorted underlying carbon networks. The inclusion of London dispersion interaction slightly affects the structure of the molecular coating but increases the adsorption energies by values as large as 0.3 eV. Interestingly, the relative stability of the previous adsorbed phases differ from the one obtained when considering single sulfur adsorption on C60, a result that reveals the crucial role played by the terminal CH3 groups on the structure of the molecular coating. The positive (negative) charging of the [C60(SCH3)n](±q) complexes, with q as large as 8e, changes the geometrical structure and the chemical nature of the ligand shell inducing lateral molecular displacements, S-S bonding between neighboring thiols, as well as the partial degradation of the molecular coating. Finally, we consider the stability of two-component mixed overlayers formed by the coadsorption of CH3-, OH-, and NH2-terminated alkanethiols of the same length. In agreement with the results found on Au surfaces, we obtain lowest energy atomic configurations when molecular domains of a single component are stabilized on C60, a result that could be of

  8. 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.

  9. Molecular orientation and lattice ordering of C60 molecules on the polar FeO/Pt(111) surface.

    PubMed

    Qin, Zhihui; Liu, Cunding; Chen, Jian; Guo, Qinmin; Yu, Yinghui; Cao, Gengyu

    2012-01-14

    C(60) molecules assemble into close packing layer under the domination of the intermolecular interaction when deposited onto Pt(111)-supported FeO layer kept at 400 K. From corresponding high resolution scanning tunneling microscopy (STM) image, a kind of C(60) molecular orientational ordering stabilized by the intermolecular interaction is revealed as C(60)/FeO(111)-(√133 × √133) R17.5° structure and determined from the commensurability between the C(60) nearest-neighbor distance and the lattice of the underlying oxygen layer. Moreover, due to the inhomogeneously distributed work function of the underlying FeO layer, the C(60) molecular electronic state is periodically modulated resulting in a bright-dim STM contrast. In addition, one coincidence lattice ordering is determined as 8 × 8 superstructure with respect to the C(60) primitive cell, which overlays a 3 × 3 moiré cell of the underlying FeO layer.

  10. Molecular orientation and lattice ordering of C60 molecules on the polar FeO/Pt(111) surface

    NASA Astrophysics Data System (ADS)

    Qin, Zhihui; Liu, Cunding; Chen, Jian; Guo, Qinmin; Yu, Yinghui; Cao, Gengyu

    2012-01-01

    C60 molecules assemble into close packing layer under the domination of the intermolecular interaction when deposited onto Pt(111)-supported FeO layer kept at 400 K. From corresponding high resolution scanning tunneling microscopy (STM) image, a kind of C60 molecular orientational ordering stabilized by the intermolecular interaction is revealed as C60/FeO(111)-(√133 × √133) R17.5° structure and determined from the commensurability between the C60 nearest-neighbor distance and the lattice of the underlying oxygen layer. Moreover, due to the inhomogeneously distributed work function of the underlying FeO layer, the C60 molecular electronic state is periodically modulated resulting in a bright-dim STM contrast. In addition, one coincidence lattice ordering is determined as 8 × 8 superstructure with respect to the C60 primitive cell, which overlays a 3 × 3 moiré cell of the underlying FeO layer.

  11. 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.

  12. Hydrophobic Porous Material Adsorbs Small Organic Molecules

    NASA Technical Reports Server (NTRS)

    Sharma, Pramod K.; Hickey, Gregory S.

    1994-01-01

    Composite molecular-sieve material has pore structure designed specifically for preferential adsorption of organic molecules for sizes ranging from 3 to 6 angstrom. Design based on principle that contaminant molecules become strongly bound to surface of adsorbent when size of contaminant molecules is nearly same as that of pores in adsorbent. Material used to remove small organic contaminant molecules from vacuum systems or from enclosed gaseous environments like closed-loop life-support systems.

  13. Cooperative Jahn-Teller effect in a 2D mesoscopic C{60/n-} system with D5d symmetry adsorbed on buffer layers using Ising EFT model

    NASA Astrophysics Data System (ADS)

    Abou Ghantous, M.; Moujaes, E. A.; Dunn, J. L.; Khater, A.

    2012-06-01

    Fullerene molecules adsorbed on surfaces often show macroscopic average distortions. As charged ions C60n- are known to be Jahn-Teller (JT) active, it is suggested that these distortions could be a manifestation of cooperative JT effects (CJTE) due to interactions between neighbouring fullerene ions. In order to understand the distortion properties it is necessary to take correlations between different distortions into account. However, this can't easily be done in the mean field approximation usually used to describe the CJTE. We therefore propose an alternative procedure to describe 2D mesoscopic islands of C60 ions in which a pseudo vector spin overrightarrow{S} is evoked to represent degenerate JT-distorted states when the quadratic JT coupling is considered. This approach is analogous to methods used for 2D magnetic systems. We then use the differential operator technique in effective field theory within the Ising approach. We include the effects of weak surface interactions and dynamic motion between equivalent distortions via terms equivalent to anisotropy and a transverse field in magnetism respectively. For distortions to D5d symmetry, we determine single site correlations as a function of temperature, the macroscopic average distortion describing a structural phase transition, and the isothermal response function. Phase diagrams are presented for relevant cases of the system parameters.

  14. 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.

  15. Thermal conductance and thermoelectric figure of merit of C60-based single-molecule junctions: Electrons, phonons, and photons

    NASA Astrophysics Data System (ADS)

    Klöckner, J. C.; Siebler, R.; Cuevas, J. C.; Pauly, F.

    2017-06-01

    Motivated by recent experiments, we present here an ab initio study of the impact of the phonon transport on the thermal conductance and thermoelectric figure of merit of C60-based single-molecule junctions. To be precise, we combine density functional theory with nonequilibrium Green's-function techniques to compute these two quantities in junctions with either a C60 monomer or a C60 dimer connected to gold electrodes, taking into account the contributions of both electrons and phonons. Our results show that for C60 monomer junctions phonon transport plays a minor role in the thermal conductance and, in turn, in the figure of merit, which can reach values on the order of 0.1, depending on the contact geometry. In C60 dimer junctions, phonons are transported less efficiently, but they completely dominate the thermal conductance and reduce the figure of merit as compared to monomer junctions. Thus, claims that by stacking C60 molecules one could achieve high thermoelectric performance, which have been made without considering the phonon contribution, are not justified. Moreover, we analyze the relevance of near-field thermal radiation for the figure of merit of these junctions within the framework of fluctuational electrodynamics. We conclude that photon tunneling can be another detrimental factor for the thermoelectric performance, which has been overlooked so far in the field of molecular electronics. Our study illustrates the crucial roles that phonon transport and photon tunneling can play, when critically assessing the performance of molecular junctions as potential nanoscale thermoelectric devices.

  16. 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

  17. Si-C 60-Si (111)-(7 × 7) interactions: a scanning tunneling microscopy study

    NASA Astrophysics Data System (ADS)

    Chen, Dong; Chen, Jian; Sarid, Dror

    1994-12-01

    Scanning tunneling microscopy (STM) has been used to study the interaction of deposited silicon atoms with C 60 molecules adsorbed on Si(111)-(7 × 7) surfaces. In spite of the known strong bonding of C 60 molecules to the silicon surfaces, we find the unexpected result of lack of bonding of the deposited silicon atoms to the adsorbed C 60 molecules, at temperatures up to 600°C. The strong C 60-substrate interaction is revealed from the excessive substrate surface strain induced by the C 60 adsorbates, which creates a variety of metastable structures on the silicon surface.

  18. Interaction of energetic clusters (Au 3, Au 400 and C 60) with organic material and adsorbed gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Restrepo, Oscar A.; Prabhakaran, Aneesh; Delcorte, Arnaud

    2011-07-01

    Using molecular dynamics simulations (MD), this contribution compares the interaction of three energetic clusters (Au3, Au400 and C60) with a hybrid surface of crystalline polyethylene (PE) covered by a layer of gold nanoparticles. This model system mimics the situation encountered in metal-assisted secondary ion mass spectrometry. The chosen impact points are representative of the PE surface, the metal particles and the frontier between the metal and the polymer. The simulations show the differences between the impact over the Au nanoparticle and the polymer surface, in terms of projectile penetration, crater formation and sputtering yield of PE and gold species. For C60 and Au3 projectiles, a simple correlation is found between the quantity of energy deposited in the top polymeric layers and the quantity of sputtered polymer material, including all the impact points. The results obtained with Au400 do not fit on this line, indicating that other physical parameters are prevalent. The mechanistic view of the interaction provided by the MD helps explain the differences. In short, while C60 and Au3 quickly break apart, creating energetic recoils and severing many bonds in the surface, Au400, with the largest total momentum by far (∼10 times larger than the others) and the lowest energy per atom (25 eV), tends to act and implant in the solid as a single entity, pushing the polymeric material downwards and breaking few bonds in the surface.

  19. Size selective hydrophobic adsorbent for organic molecules

    NASA Technical Reports Server (NTRS)

    Sharma, Pramod K. (Inventor); Hickey, Gregory S. (Inventor)

    1997-01-01

    The present invention relates to an adsorbent formed by the pyrolysis of a hydrophobic silica with a pore size greater than 5 .ANG., such as SILICALITE.TM., with a molecular sieving polymer precursor such as polyfurfuryl alcohol, polyacrylonitrile, polyvinylidene chloride, phenol-formaldehyde resin, polyvinylidene difluoride and mixtures thereof. Polyfurfuryl alcohol is the most preferred. The adsorbent produced by the pyrolysis has a silicon to carbon mole ratio of between about 10:1 and 1:3, and preferably about 2:1 to 1:2, most preferably 1:1. The pyrolysis is performed as a ramped temperature program between about 100.degree. and 800.degree. C., and preferably between about 100.degree. and 600.degree. C. The present invention also relates to a method for selectively adsorbing organic molecules having a molecular size (mean molecular diameter) of between about 3 and 6 .ANG. comprising contacting a vapor containing the small organic molecules to be adsorbed with the adsorbent composition of the present invention.

  20. Single-molecule measurements of adsorbed polymer

    NASA Astrophysics Data System (ADS)

    Yu, Changqian; Guan, Juan; Bae, Sung Chul; Granick, Steve

    2011-03-01

    Single-molecule tracking is used to study the surface mobility of PEG (polyethylene glycol) chains adsorbed to the solid-liquid interface from dilute aqueous solution. The end-labeled chains are visualized by objective-based total internal reflection fluorescence microscopy (TIRFM) and their trajectories are analyzed after cleaning the images with denoising algorithms. Surface mobility, which in this system depends on pH, is decomposed into one family of chains which remains adsorbed over the observation time window, and another family that appears to translate from point to point by hopping. This we quantify with nm-level resolution.

  1. Imaging the wave functions of adsorbed molecules.

    PubMed

    Lüftner, Daniel; Ules, Thomas; Reinisch, Eva Maria; Koller, Georg; Soubatch, Serguei; Tautz, F Stefan; Ramsey, Michael G; Puschnig, Peter

    2014-01-14

    The basis for a quantum-mechanical description of matter is electron wave functions. For atoms and molecules, their spatial distributions and phases are known as orbitals. Although orbitals are very powerful concepts, experimentally only the electron densities and -energy levels are directly observable. Regardless whether orbitals are observed in real space with scanning probe experiments, or in reciprocal space by photoemission, the phase information of the orbital is lost. Here, we show that the experimental momentum maps of angle-resolved photoemission from molecular orbitals can be transformed to real-space orbitals via an iterative procedure which also retrieves the lost phase information. This is demonstrated with images obtained of a number of orbitals of the molecules pentacene (C22H14) and perylene-3,4,9,10-tetracarboxylic dianhydride (C24H8O6), adsorbed on silver, which are in excellent agreement with ab initio calculations. The procedure requires no a priori knowledge of the orbitals and is shown to be simple and robust.

  2. Scattering Properties of Gas Molecules on a Water Adsorbed Surface

    NASA Astrophysics Data System (ADS)

    Takeuchi, Hideki; Yamamoto, Kyoji; Hyakutake, Toru

    2011-05-01

    The thermal problem of a rarefied argon (Ar) gas between two parallel walls is considered to investigate the characteristics of the reflected gas molecule at a platinum (Pt) wall surface which physically adsorbs water (H2O) molecules. The analysis is based on the molecular dynamics (MD) method for the interaction of gas molecules with the water adsorbed wall surface together with the direct simulation Monte-Carlo (DSMC) method for the motion of gas molecule. The accommodation coefficients of energy and normal momentum are obtained. The temperature distribution between two walls and the velocity distribution function of the reflected molecule are also obtained. It is found that the accommodation coefficients for the water adsorbed surface decrease with increasing the adsorption rate.

  3. Chiral switching by spontaneous conformational change in adsorbed organic molecules.

    PubMed

    Weigelt, Sigrid; Busse, Carsten; Petersen, Lars; Rauls, Eva; Hammer, Bjørk; Gothelf, Kurt V; Besenbacher, Flemming; Linderoth, Trolle R

    2006-02-01

    Self-assembly of adsorbed organic molecules is a promising route towards functional surface nano-architectures, and our understanding of associated dynamic processes has been significantly advanced by several scanning tunnelling microscopy (STM) investigations. Intramolecular degrees of freedom are widely accepted to influence ordering of complex adsorbates, but although molecular conformation has been identified and even manipulated by STM, the detailed dynamics of spontaneous conformational change in adsorbed molecules has hitherto not been addressed. Molecular surface structures often show important stereochemical effects as, aside from truly chiral molecules, a large class of so-called prochiral molecules become chiral once confined on a surface with an associated loss of symmetry. Here, we investigate a model system in which adsorbed molecules surprisingly switch between enantiomeric forms as they undergo thermally induced conformational changes. The associated kinetic parameters are quantified from time-resolved STM data whereas mechanistic insight is obtained from theoretical modelling. The chiral switching is demonstrated to enable an efficient channel towards formation of extended homochiral surface domains. Our results imply that appropriate prochiral molecules may be induced (for example, by seeding) to assume only one enantiomeric form in surface assemblies, which is of relevance for chiral amplification and asymmetric heterogenous catalysis.

  4. Adsorbed molecules in external fields: Effect of confining potential.

    PubMed

    Tyagi, Ashish; Silotia, Poonam; Maan, Anjali; Prasad, Vinod

    2016-12-05

    We study the rotational excitation of a molecule adsorbed on a surface. As is well known the interaction potential between the surface and the molecule can be modeled in number of ways, depending on the molecular structure and the geometry under which the molecule is being adsorbed by the surface. We explore the effect of change of confining potential on the excitation, which is largely controlled by the static electric fields and continuous wave laser fields. We focus on dipolar molecules and hence we restrict ourselves to the first order interaction in field-molecule interaction potential either through permanent dipole moment or/and the molecular polarizability parameter. It is shown that confining potential shapes, strength of the confinement, strongly affect the excitation. We compare our results for different confining potentials.

  5. Adsorbed molecules in external fields: Effect of confining potential

    NASA Astrophysics Data System (ADS)

    Tyagi, Ashish; Silotia, Poonam; Maan, Anjali; Prasad, Vinod

    2016-12-01

    We study the rotational excitation of a molecule adsorbed on a surface. As is well known the interaction potential between the surface and the molecule can be modeled in number of ways, depending on the molecular structure and the geometry under which the molecule is being adsorbed by the surface. We explore the effect of change of confining potential on the excitation, which is largely controlled by the static electric fields and continuous wave laser fields. We focus on dipolar molecules and hence we restrict ourselves to the first order interaction in field-molecule interaction potential either through permanent dipole moment or/and the molecular polarizability parameter. It is shown that confining potential shapes, strength of the confinement, strongly affect the excitation. We compare our results for different confining potentials.

  6. Extended surface chirality from supramolecular assemblies of adsorbed chiral molecules

    NASA Astrophysics Data System (ADS)

    Ortega Lorenzo, M.; Baddeley, C. J.; Muryn, C.; Raval, R.

    2000-03-01

    The increasing demand of the chemical and pharmaceutical industries for enantiomerically pure compounds has spurred the development of a range of so-called `chiral technologies' (ref. 1), which aim to exert the ultimate control over a chemical reaction by directing its enantioselectivity. Heterogeneous enantioselective catalysis is particularly attractive because it allows the production and ready separation of large quantities of chiral product while using only small quantities of catalyst. Heterogeneous enantioselectivity is usually induced by adsorbing chiral molecules onto catalytically active surfaces. A mimic of one such catalyst is formed by adsorbing (R,R)-tartaric acid molecules on Cu(110) surfaces: this generates a variety of surface phases, of which only one is potentially catalytically active, and leaves the question of how adsorbed chiral molecules give rise to enantioselectivity. Here we show that the active phase consists of extended supramolecular assemblies of adsorbed (R,R)-tartaric acid, which destroy existing symmetry elements of the underlying metal and directly bestow chirality to the modified surface. The adsorbed assemblies create chiral `channels' exposing bare metal atoms, and it is these chiral spaces that we believe to be responsible for imparting enantioselectivity, by forcing the orientation of reactant molecules docking onto catalytically active metal sites. Our findings demonstrate that it is possible to sustain a single chiral domain across an extended surface-provided that reflection domains of opposite handedness are removed by a rigid and chiral local adsorption geometry, and that inequivalent rotation domains are removed by successful matching of the rotational symmetry of the adsorbed molecule with that of the underlying metal surface.

  7. Forces from periodic charging of adsorbed molecules

    NASA Astrophysics Data System (ADS)

    Kocić, N.; Decurtins, S.; Liu, S.-X.; Repp, J.

    2017-03-01

    In a recent publication [Kocić et al., Nano Lett. 15, 4406 (2015)], it was shown that gating of molecular levels in the field of an oscillating tip of an atomic force microscope can enable a periodic charging of individual molecules synchronized to the tip's oscillatory motion. Here we discuss further implications of such measurements, namely, how the force difference associated with the single-electron charging manifests itself in atomic force microscopy images and how it can be detected as a function of tip-sample distance. Moreover, we discuss how the critical voltage for the charge-state transition depends on distance and how that relates to the local contact potential difference. These measurements allow also for an estimate of the absolute tip-sample distance.

  8. 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.

  9. 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

  10. Hydrogen molecule on lithium adsorbed graphene: A DFT study

    SciTech Connect

    Kaur, Gagandeep; Gupta, Shuchi; Gaganpreet; Dharamvir, Keya

    2016-05-06

    Electronic structure calculations for the adsorption of molecular hydrogen on lithium (Li) decorated and pristine graphene have been studied systematically using SIESTA code [1] within the framework of the first-principle DFT under the Perdew-Burke-Ernzerhof (PBE) form of the generalized gradient approximation (GGA)[2], including spin polarization. The energy of adsorption of hydrogen molecule on graphene is always enhanced by the presence of co-adsorbed lithium. The most efficient adsorption configuration is when H{sub 2} is lying parallel to lithium adsorbed graphene which is in contrast to its adsorption on pristine graphene (PG) where it prefers perpendicular orientation.

  11. Controlling the magnetism of adsorbed metal-organic molecules.

    PubMed

    Kuch, Wolfgang; Bernien, Matthias

    2017-01-18

    Gaining control on the size or the direction of the magnetic moment of adsorbed metal-organic molecules constitutes an important step towards the realization of a surface-mounted molecular spin electronics. Such control can be gained by taking advantage of interactions of the molecule's magnetic moment with the environment. The paramagnetic moments of adsorbed metal-organic molecules, for example, can be controlled by the interaction with magnetically ordered substrates. Metalloporphyrins and -phthalocyanines display a quasi-planar geometry, allowing the central metal ion to interact with substrate electronic states. This can lead to magnetic coupling with a ferromagnetic or even antiferromagnetic substrate. The molecule-substrate coupling can be mediated and controlled by insertion layers such as oxygen atoms, graphene, or nonmagnetic metal layers. Control on the magnetic properties of adsorbed metalloporphyrins or -phthalocyanines can also be gained by on-surface chemical modification of the molecules. The magnetic moment or the magnetic coupling to ferromagnetic substrates can be changed by adsorption and thermal desorption of small molecules that interact with the fourfold-coordinated metal center via the remaining axial coordination site. Spin-crossover molecules, which possess a metastable spin state that can be switched by external stimuli such as temperature or light, are another promising class of candidates for control of magnetic properties. However, the immobilization of such molecules on a solid surface often results in a quench of the spin transition due to the interaction with the substrate. We present examples of Fe(II) spin-crossover complexes in direct contact with a solid surface that undergo a reversible spin-crossover transition as a function of temperature, by illumination with visible light, or can be switched by the tip of a scanning tunneling microscope.

  12. Controlling the magnetism of adsorbed metal-organic molecules

    NASA Astrophysics Data System (ADS)

    Kuch, Wolfgang; Bernien, Matthias

    2017-01-01

    Gaining control on the size or the direction of the magnetic moment of adsorbed metal-organic molecules constitutes an important step towards the realization of a surface-mounted molecular spin electronics. Such control can be gained by taking advantage of interactions of the molecule’s magnetic moment with the environment. The paramagnetic moments of adsorbed metal-organic molecules, for example, can be controlled by the interaction with magnetically ordered substrates. Metalloporphyrins and -phthalocyanines display a quasi-planar geometry, allowing the central metal ion to interact with substrate electronic states. This can lead to magnetic coupling with a ferromagnetic or even antiferromagnetic substrate. The molecule-substrate coupling can be mediated and controlled by insertion layers such as oxygen atoms, graphene, or nonmagnetic metal layers. Control on the magnetic properties of adsorbed metalloporphyrins or -phthalocyanines can also be gained by on-surface chemical modification of the molecules. The magnetic moment or the magnetic coupling to ferromagnetic substrates can be changed by adsorption and thermal desorption of small molecules that interact with the fourfold-coordinated metal center via the remaining axial coordination site. Spin-crossover molecules, which possess a metastable spin state that can be switched by external stimuli such as temperature or light, are another promising class of candidates for control of magnetic properties. However, the immobilization of such molecules on a solid surface often results in a quench of the spin transition due to the interaction with the substrate. We present examples of Fe(II) spin-crossover complexes in direct contact with a solid surface that undergo a reversible spin-crossover transition as a function of temperature, by illumination with visible light, or can be switched by the tip of a scanning tunneling microscope.

  13. Candidate Source of Flux Noise in SQUIDs: Adsorbed Oxygen Molecules.

    PubMed

    Wang, Hui; Shi, Chuntai; Hu, Jun; Han, Sungho; Yu, Clare C; Wu, R Q

    2015-08-14

    A major obstacle to using superconducting quantum interference devices (SQUIDs) as qubits is flux noise. We propose that the heretofore mysterious spins producing flux noise could be O_{2} molecules adsorbed on the surface. Using density functional theory calculations, we find that an O_{2} molecule adsorbed on an α-alumina surface has a magnetic moment of ~1.8 μ_{B}. The spin is oriented perpendicular to the axis of the O-O bond, the barrier to spin rotations is about 10 mK. Monte Carlo simulations of ferromagnetically coupled, anisotropic XY spins on a square lattice find 1/f magnetization noise, consistent with flux noise in Al SQUIDs.

  14. Candidate Source of Flux Noise in SQUIDs: Adsorbed Oxygen Molecules

    NASA Astrophysics Data System (ADS)

    Wang, Hui; Shi, Chuntai; Hu, Jun; Han, Sungho; Yu, Clare C.; Wu, R. Q.

    2015-08-01

    A major obstacle to using superconducting quantum interference devices (SQUIDs) as qubits is flux noise. We propose that the heretofore mysterious spins producing flux noise could be O2 molecules adsorbed on the surface. Using density functional theory calculations, we find that an O2 molecule adsorbed on an α-alumina surface has a magnetic moment of ˜1.8 μB . The spin is oriented perpendicular to the axis of the O-O bond, the barrier to spin rotations is about 10 mK. Monte Carlo simulations of ferromagnetically coupled, anisotropic X Y spins on a square lattice find 1 /f magnetization noise, consistent with flux noise in Al SQUIDs.

  15. Resonant vibrational excitation of adsorbed molecules by electron impact

    NASA Astrophysics Data System (ADS)

    Djamo, V.; Teillet-Billy, D.; Gauyacq, J. P.

    1993-11-01

    The vibrational excitation of N2 molecules adsorbed on a silver surface by low energy electron impact is studied within the newly developed coupled angular mode method. The process involves the formation of a transient negative molecular ion. The results account well for the observations of Demuth and co-workers. They also reveal that most of the vibrational excitation corresponds to electrons scattered into the metal and thus unobservable in a scattering experiment.

  16. Surface structure of SiC formed by C60 molecules on a Si(001)-2×1 surface at 800 °C

    NASA Astrophysics Data System (ADS)

    Cheng, C.-P.; Huang, J.-W.; Pi, T.-W.; Lee, H.-H.

    2006-06-01

    Formation of silicon carbide upon deposition of C60 onto Si(001) at an elevated temperature of 800 °C was studied via synchrotron-radiation photoemission and low electron energy diffraction. The molecules are completely decomposed upon hitting on the hot surface, giving rise to a well-order 2×1 pattern. The C 1s and Si 2p core-level spectra, and valence-band spectra indicate characteristics of a Si-terminated β-SiC(001) 2×1 film. Two surface components corresponding to the terminated and ad-dimer Si atoms are well resolved in the Si 2p cores. By the spectral area ratio of both components, the adlayer atoms cover half of the surface, which agrees with the missing-row structure model [W. Lu et al., Phys. Rev. Lett. 81, 2292 (1998)].

  17. C60 on SiC nanomesh.

    PubMed

    Chen, Wei; Zhang, Hong Liang; Xu, Hai; Tok, Eng Soon; Loh, Kian Ping; Wee, Andrew Thye Shen

    2006-11-02

    A SiC nanomesh is used as a nanotemplate to direct the epitaxy of C60 molecules. The epitaxial growth of C60 molecules on SiC nanomesh at room temperature is investigated by in situ scanning tunneling microscopy, revealing a typical Stranski-Krastanov mode (i.e., for the first one or two monolayers, it is a layer-by-layer growth or 2-D nucleation mode; at higher thicknesses, it changes to island growth or a 3-D nucleation mode). At submonolayer (0.04 and 0.2 ML) coverage, C60 molecules tend to aggregate to form single-layer C60 islands that mainly decorate terrace edges, leaving the uncovered SiC nanomesh almost free of C60 molecules. At 1 ML C60 coverage, a complete wetting layer of hexagonally close-packed C60 molecules forms on top of the SiC nanomesh. At higher coverage from 4.5 ML onward, the C60 stacking adopts a (111) oriented face-centered-cubic (fcc) structure. Strong bright and dim molecular contrasts have been observed on the first layer of C60 molecules, which are proposed to originate from electronic effects in a single-layer C60 island or the different coupling of C60 molecules to SiC nanomesh. These STM molecular contrast patterns completely disappear on the second and all the subsequent C60 layers. It is also found that the nanomesh can be fully recovered by annealing the C60/SiC nanomesh sample at 200 degrees C for 20 min.

  18. SPR-MS: from identifying adsorbed molecules to image tissues

    NASA Astrophysics Data System (ADS)

    Masson, Jean-François; Breault-Turcot, Julien; Forest, Simon; Chaurand, Pierre

    2015-03-01

    Surface plasmon resonance (SPR) sensors have become valuable analytical sensors for biomolecule detection. While SPR is heralded with high sensitivity, label-free and real-time detection, nonspecific adsorption and detection of ultralow concentrations remain issues. Nonspecific adsorption can be minimized using adequate surface chemistry. For example, we have employed peptide monolayers to reduce nonspecific adsorption of crude serum or cell lysate. It is important to uncover the nature of molecules nonspecifically adsorbing to surfaces in these biofluids, to further improve understanding of the nonspecific adsorption processes. Mass spectrometry (MS) provides a complementary tool to SPR to identify biomolecule adsorbed to surface. Trypsic digestion of the proteins adsorbed to surfaces led to identification of characteristic peptides from the proteins involved in nonspecific adsorption. Nonspecific adsorption in crude cell lysate results mainly from lipids, as confirmed with SPR and MS but proteins were observed on some surfaces. In another application of SPR and MS, imaging SPR can be used in combination to imaging MS to image tissue sections. Thin sections of mouse liver were inserted in the fluidic chamber of a SPRi instrument and proteins were transferred to the SPRi chip. The SPR chip was then imaged using MALDI imaging MS to identify the biomolecules that were transferred to the SPRi chip.

  19. Multiple species of noninteracting molecules adsorbed on a Bethe lattice.

    PubMed

    Cohen, Michael; Harris, A B

    2008-10-01

    A simple method, previously used to calculate the equilibrium concentration of dimers adsorbed on a Bethe lattice as a function of the dimer activity, is generalized to solve the problem of a Bethe lattice in contact with a reservoir containing a mixture of molecules. The molecules may have arbitrary sizes and shapes consistent with the geometry of the lattice and the molecules do not interact with one another except for the hard-core restriction that two molecules cannot touch the same site. We obtain a set of simultaneous nonlinear equations, one equation for each species of molecule, which determines the equilibrium concentration of each type of molecule as a function of the (arbitrary) activities of the various species. Surprisingly, regardless of the number of species, the equilibrium concentrations are given explicitly in terms of the solution of a single equation in one unknown which can be solved numerically, if need be. Some numerical examples show that increasing the activity of one species need not necessarily decrease the equilibrium concentration of all other species. We also calculate the adsorption isotherm of an "annealed" Bethe lattice consisting of two types of sites which differently influence the activity of an adsorbed molecule. We prove that if the reservoir contains a finite number of molecular species, regions of two different polymer densities cannot simultaneously exist on the lattice. The widely used Guggenheim theory of mixtures, which can also be construed as a theory of adsorption, assumes for simplicity that the molecules in the mixture are composed of elementary units, which occupy sites of a lattice of coordination number q . Guggenheim's analysis relies on approximate combinatorial formulas which become exact on a Bethe lattice of the same coordination number, as we show in an appendix. Our analysis involves no combinatorics and relies only on recognizing the statistical independence of certain quantities. Despite the nominal

  20. An STM study of C 60 adsorption on Si(100)-(2 × 1) surfaces: from physisorption to chemisorption

    NASA Astrophysics Data System (ADS)

    Chen, Dong; Sarid, Dror

    1995-05-01

    The adsorption of C 60 molecules on Si(100)-(2 × 1) surfaces before and after annealing has been studied using scanning tunneling microscopy (STM). For room temperature deposition, the STM images reveal that the C 60 molecules adsorb predominantly at the four-dimer sites in the troughs between dimer rows. C 60 molecules bonded to two-dimer sites are also observed in small molecular clusters forming even at a low coverage. The nature of the interaction between the adsorbates and the Si(100)-(2 × 1) surface is explained in terms of a dipole-induced dipole interaction. Subsequent annealing of the samples to 600°C changes the adsorption characteristics of the C 60 molecules. First, the annealing causes a strong covalent bonding between the carbon atoms of the C 60 molecules and the silicon atoms of the substrate, and modifies the bonding sites of the adsorbates from locations in the troughs to locations on the dimer rows. Second, the annealing causes some initial surface diffusion and clustering of the C 60 molecules, which now tend to stick to the ends, rather than the sides, of the dimer rows. Furthermore, after the annealing process, it is observed that small silicon islands form on the substrate terraces along with isolated and clustered adsorbates.

  1. Carbonaceous molecules in the oxygen-rich circumstellar environment of binary post-AGB stars. C60 fullerenes and polycyclic aromatic hydrocarbons

    NASA Astrophysics Data System (ADS)

    Gielen, C.; Cami, J.; Bouwman, J.; Peeters, E.; Min, M.

    2011-12-01

    Context. The circumstellar environment of evolved stars is generally rich in molecular gas and dust. Typically, the entire environment is either oxygen-rich or carbon-rich, depending on the evolution of the central star. Aims: In this paper we discuss three evolved disc sources with evidence of atypical emission lines in their infrared spectra. The stars were taken from a larger sample of post-AGB binaries for which we have Spitzer infrared spectra, characterised by the presence of a stable oxygen-rich circumbinary disc. Our previous studies have shown that the infrared spectra of post-AGB disc sources are dominated by silicate dust emission, often with an extremely high crystallinity fraction. However, the three sources described here are selected because they show a peculiar molecular chemistry. Methods: Using Spitzer infrared spectroscopy, we study in detail the peculiar mineralogy of the three sample stars. Using the observed emission features, we identify the different observed dust, molecular and gas species. Results: The infrared spectra show emission features due to various oxygen-rich dust components, as well as CO2 gas. All three sources show the strong infrared bands generally ascribed to polycyclic aromatic hydrocarbons. Furthermore, two sample sources show C60 fullerene bands. Conclusions: Even though the majority of post-AGB disc sources are dominated by silicate dust in their circumstellar environment, we do find evidence that, for some sources at least, additional processing must occur to explain the presence of large carbonaceous molecules. There is evidence that some of these sources are still oxygen-rich, which makes the detection of these molecules even more surprising. This research has made use of the SIMBAD database, operated at CDS, Strasbourg, France. Based on observations made with the Spitzer Space Telescope (program id 3274, 50092), which is operated by the Jet Propulsion Laboratory, California Institute of Technology under a contract

  2. Detection of individual gas molecules adsorbed on graphene.

    PubMed

    Schedin, F; Geim, A K; Morozov, S V; Hill, E W; Blake, P; Katsnelson, M I; Novoselov, K S

    2007-09-01

    The ultimate aim of any detection method is to achieve such a level of sensitivity that individual quanta of a measured entity can be resolved. In the case of chemical sensors, the quantum is one atom or molecule. Such resolution has so far been beyond the reach of any detection technique, including solid-state gas sensors hailed for their exceptional sensitivity. The fundamental reason limiting the resolution of such sensors is fluctuations due to thermal motion of charges and defects, which lead to intrinsic noise exceeding the sought-after signal from individual molecules, usually by many orders of magnitude. Here, we show that micrometre-size sensors made from graphene are capable of detecting individual events when a gas molecule attaches to or detaches from graphene's surface. The adsorbed molecules change the local carrier concentration in graphene one by one electron, which leads to step-like changes in resistance. The achieved sensitivity is due to the fact that graphene is an exceptionally low-noise material electronically, which makes it a promising candidate not only for chemical detectors but also for other applications where local probes sensitive to external charge, magnetic field or mechanical strain are required.

  3. Controlling spins in adsorbed molecules by a chemical switch

    PubMed Central

    Wäckerlin, Christian; Chylarecka, Dorota; Kleibert, Armin; Müller, Kathrin; Iacovita, Cristian; Nolting, Frithjof; Jung, Thomas A.; Ballav, Nirmalya

    2010-01-01

    The development of chemical systems with switchable molecular spins could lead to the architecture of materials with controllable magnetic or spintronic properties. Here, we present conclusive evidence that the spin of an organometallic molecule coupled to a ferromagnetic substrate can be switched between magnetic off and on states by a chemical stimulus. This is achieved by nitric oxide (NO) functioning as an axial ligand of cobalt(II)tetraphenylporphyrin (CoTPP) ferromagnetically coupled to nickel thin-film (Ni(001)). On NO addition, the coordination sphere of Co2+ is modified and a NO–CoTPP nitrosyl complex is formed, which corresponds to an off state of the Co spin. Thermal dissociation of NO from the nitrosyl complex restores the on state of the Co spin. The NO-induced reversible off–on switching of surface-adsorbed molecular spins observed here is attributed to a spin trans effect. PMID:20975713

  4. An Ab Initio Study of Alkali-C60 Complexes

    NASA Astrophysics Data System (ADS)

    Frick, Nathan; Hira, A. S.; Ray, A. K.

    2003-03-01

    We extend our previous work on fullerene-alkali complexes1-2 by presenting the results of an ab initio theoretical study of the alkali LiC60+, LiC60, NaC60+, NaC60, KC60+, and KC60 complexes. In the endohedral complexes for Li and Na, there is displacement of the adatom from the center. Of the ions, exohedral Li+ will sit closest to the cage, and among the neutrals, exohedral K remains closest. Bond lengths are consistently longer for the fivefold and threefold approaches. Adsorbates inside the fullerene donate negative charge to the carbons, but ions outside obtain a small amount, resulting in a polarization of the molecule. In the ion complexes, there is lowering of the orbital energy levels by 3 to 4 eV, resulting in an increase in the number of bound, but unoccupied, electronic orbitals. The HOMO-LUMO gap, of interest in superconductivity studies, is reduced by about 50 1. A.S. Hira and A.K. Ray, Phys. Rev. A 52, 141(1995); A 54, 2205(1996). 2. Ajit Hira and A. K. Ray, "An Initio Modeling of the Endohedral and Exohedral Complexes of C60Na2+ Complexes", Bull. Am. Phys. Soc. 47 (March 2002).

  5. Hydrogen Diffusion in C_60

    NASA Astrophysics Data System (ADS)

    Fitzgerald, Stephen; Sethna, Dorab; Szuts, Zoltan

    2001-03-01

    Recently^1 it has been shown that hydrogen molecules can be forced into a C_60 lattice under modest pressure. A loading pressure of 2,000 PSI is sufficient to fill almost 50 % of the available octahedral sites. Here we extend this work to consider the kinetics of the hydrogen diffusion within the C_60 lattice. In our procedure the sample is first loaded to its equilibrium H2 concentration. The confining pressure is then quickly removed and the rate at which the H2 outgasses from the powder is monitored via the slow pressure increase with time. Results show that the outgassing time constant depends critically on the particle sized distribution of the C_60. Ground powders have time-constants almost an order of magnitude faster than unground. In all cases the kinetics are consistent with a two-time constant model in which the hydrogen diffuses within the lattice and along the grain boundaries between crystallites. However, the loaded H2 concentration depends solely on the loading pressure independent of the powder type indicating that at equilibrium the H2 molecules reside exclusively at the lattice octahedral sites and not in the grain boundaries. Measurements taken at a series of different temperatures indicate that diffusion within the lattice has an activation barrier of 105 meV. This compares well with the theoretical predictions for the octahedral well depth of 110 meV^1. ^1 S. A. FitzGerald et al., Phys. Rev. B 60, 6439 (1999).

  6. Spatial distribution of protein molecules adsorbed at a polyelectrolyte multilayer

    NASA Astrophysics Data System (ADS)

    Jackler, Guido; Czeslik, Claus; Steitz, Roland; Royer, Catherine A.

    2005-04-01

    The spatial distribution of protein molecules interacting with a planar polyelectrolyte multilayer was determined using neutron reflectometry. Staphylococcal nuclease (SNase) was used as model protein that was adsorbed to the multilayer at 22°C and 42°C . At each temperature, the protein solution was adjusted to pD -values of 4.9 and 7.5 to vary the net charge of the protein molecules. The multilayer was built up on a silicon wafer by the deposition of poly(ethylene imine) (PEI), poly(styrene sulfonate) (PSS), and poly(allylamine hydrochloride) (PAH) in the order Si-PEI-PSS- (PAH-PSS)5 . Applying the contrast variation technique, two different neutron reflectivity curves were measured at each condition of temperature and pD -value. From the analysis of the curves, protein density profiles normal to the interface were recovered. Remarkably, it has been found that SNase is partially penetrating into the polyelectrolyte multilayer after adsorption at all conditions studied. The measured neutron reflectivities are consistent with a penetration depth of 50Å at pD=4.9 and 25Å at pD=7.5 . Since SNase has an isoelectric point of pH=9.5 , it carries a net positive charge at both pD -values and interacts with the PSS final layer under electrostatic attraction conditions. However, when increasing the temperature, the amount of adsorbed protein is increasing at both pD -values indicating the dominance of entropic driving forces for the protein adsorption. Interestingly, at pD=4.9 where the protein charge is relatively high, this temperature-induced mass increase of immobilized protein is more pronounced within the polyelectrolyte multilayer, whereas at pD=7.5 , closer to the isoelectric point of SNase, raising the temperature has mainly the effect to accumulate protein molecules outside the polyelectrolyte multilayer at the water interface. It is suggested that the penetration of SNase into the polyelectrolyte multilayer is related to a complexation mechanism. The

  7. Translocation mechanism of C60 and C60 derivations across a cell membrane

    NASA Astrophysics Data System (ADS)

    Liang, Lijun; Kang, Zhengzhong; Shen, Jia-Wei

    2016-11-01

    Carbon-based nanoparticles (NPs) such as fullerenes and nanotubes have been extensively studied for drug delivery in recent years. The permeation process of fullerene and its derivative molecules through membrane is essential to the utilization of fullerene-based drug delivery system, but the mechanism and the dynamics of permeation through cell membrane are still unclear. In this study, coarse-grained molecular dynamics simulations were performed to investigate the permeation process of functionalized fullerene molecules (ca. 0.72 nm) through the membrane. Our results show that single functionalized fullerene molecule in such nanoscale could permeate the lipid membrane in micro-second time scale. Pristine C60 molecules prefer to aggregate into several small clusters while C60OH15 molecules could aggregate into one big cluster to permeate through the lipid membrane. After permeation of C60 or its derivatives into membrane, all C60 and C60OH15 molecules disaggregated and monodispersed in the lipid membrane.

  8. Using the graphene Moiré pattern for the trapping of C60 and homoepitaxy of graphene.

    PubMed

    Lu, Jiong; Yeo, Pei Shan Emmeline; Zheng, Yi; Yang, Zhiyong; Bao, Qiaoliang; Gan, Chee Kwan; Loh, Kian Ping

    2012-01-24

    The graphene Moiré superstructure offers a complex landscape of humps and valleys to molecules adsorbing and diffusing on it. Using C(60) molecules as the classic hard sphere analogue, we examine its assembly and layered growth on this corrugated landscape. At the monolayer level, the cohesive interactions of C(60) molecules adsorbing on the Moiré lattice freeze the molecular rotation of C(60) trapped in the valley sites, resulting in molecular alignment of all similarly trapped C(60) molecules at room temperature. The hierarchy of adsorption potential well on the Moiré lattice causes diffusion-limited dendritic growth of C(60) films, as opposed to isotropic growth observed on a smooth surface like graphite. Due to the strong binding energy of the C(60) film, part of the dentritic C(60) films polymerize at 850 K and act as solid carbon sources for graphene homoepitaxy. Our findings point to the possibility of using periodically corrugated graphene in molecular spintronics due to its ability to trap and align organic molecules at room temperature.

  9. Polarizabilities of Adsorbed and Assembled Molecules: Measuring the Conductance through Buried Contacts

    PubMed Central

    2010-01-01

    We have measured the polarizabilities of four families of molecules adsorbed to Au{111} surfaces, with structures ranging from fully saturated to fully conjugated, including single-molecule switches. Measured polarizabilities increase with increasing length and conjugation in the adsorbed molecules and are consistent with theoretical calculations. For single-molecule switches, the polarizability reflects the difference in substrate−molecule electronic coupling in the ON and OFF conductance states. Calculations suggest that the switch between the two conductance states is correlated with an oxidation state change in a nitro functional group in the switch molecules. PMID:21077677

  10. 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.

  11. Procedure for freeze-drying molecules adsorbed to mica flakes.

    PubMed

    Heuser, J E

    1983-09-05

    The quick-freeze, deep-etch, rotary-replication technique is useful for visualizing cells and cell fractions but does not work with suspensions of macromolecules. These inevitably clump or collapse during deep-etching, presumably due to surface tension forces that develop during their transfer from ice to vacuum. Previous protocols have attempted to overcome such forces by attaching macromolecules to freshly cleaved mica before drying and replication. I describe here an adaptation of this procedure to the deep-etch technique as otherwise practiced. My innovation is to mix the molecules with an aqueous suspension of tiny flakes of mica and then to quick-freeze and freeze-fracture the suspension exactly as if one were dealing with cells. The fracture inevitably strikes the surfaces of many mica flakes and thereby cleaves the adsorbed macromolecules cleanly enough to reveal interesting substructure within them. The subsequent step of deep-etching exposes large expanses of unfractured mica and thus reveals intact macromolecules. These macromolecules are not obscured by salt deposits, even if they were frozen in hypertonic solutions, apparently because the fracturing step removes nearly all of the overlying electrolyte. Moreover, these macromolecules are minimally freeze-dried (since exposure is sufficient after only 3 min of etching at -102 degrees C) so they retain their three-dimensional topology. I show that molluscan hemocyanin is a good internal standard for this new technique. It is available commercially in stable solutions, mixes well with all sizes of macromolecules, and consists of particles that display distinct five-start surface helices, which have been measured carefully in the past and which possess a known handedness, useful for determining the orientation of micrographs when examining the various helical patterns possessed by most types of extended macromolecules. The fractured hemocyanin particles also display characteristic internal structures, which

  12. The dipolar endofullerene HF@C60

    NASA Astrophysics Data System (ADS)

    Krachmalnicoff, Andrea; Bounds, Richard; Mamone, Salvatore; Alom, Shamim; Concistrè, Maria; Meier, Benno; Kouřil, Karel; Light, Mark E.; Johnson, Mark R.; Rols, Stéphane; Horsewill, Anthony J.; Shugai, Anna; Nagel, Urmas; Rõõm, Toomas; Carravetta, Marina; Levitt, Malcolm H.; Whitby, Richard J.

    2016-10-01

    The cavity inside fullerenes provides a unique environment for the study of isolated atoms and molecules. We report the encapsulation of hydrogen fluoride inside C60 using molecular surgery to give the endohedral fullerene HF@C60. The key synthetic step is the closure of the open fullerene cage with the escape of HF minimized. The encapsulated HF molecule moves freely inside the cage and exhibits quantization of its translational and rotational degrees of freedom, as revealed by inelastic neutron scattering and infrared spectroscopy. The rotational and vibrational constants of the encapsulated HF molecules were found to be redshifted relative to free HF. The NMR spectra display a large 1H-19F J coupling typical of an isolated species. The dipole moment of HF@C60 was estimated from the temperature dependence of the dielectric constant at cryogenic temperatures and showed that the cage shields around 75% of the HF dipole.

  13. The dipolar endofullerene HF@C60.

    PubMed

    Krachmalnicoff, Andrea; Bounds, Richard; Mamone, Salvatore; Alom, Shamim; Concistrè, Maria; Meier, Benno; Kouřil, Karel; Light, Mark E; Johnson, Mark R; Rols, Stéphane; Horsewill, Anthony J; Shugai, Anna; Nagel, Urmas; Rõõm, Toomas; Carravetta, Marina; Levitt, Malcolm H; Whitby, Richard J

    2016-10-01

    The cavity inside fullerenes provides a unique environment for the study of isolated atoms and molecules. We report the encapsulation of hydrogen fluoride inside C60 using molecular surgery to give the endohedral fullerene HF@C60. The key synthetic step is the closure of the open fullerene cage with the escape of HF minimized. The encapsulated HF molecule moves freely inside the cage and exhibits quantization of its translational and rotational degrees of freedom, as revealed by inelastic neutron scattering and infrared spectroscopy. The rotational and vibrational constants of the encapsulated HF molecules were found to be redshifted relative to free HF. The NMR spectra display a large (1)H-(19)F J coupling typical of an isolated species. The dipole moment of HF@C60 was estimated from the temperature dependence of the dielectric constant at cryogenic temperatures and showed that the cage shields around 75% of the HF dipole.

  14. C60 in Photodissociation Regions

    NASA Astrophysics Data System (ADS)

    Castellanos, Pablo; Berné, Olivier; Sheffer, Yaron; Wolfire, Mark G.; Tielens, Alexander G. G. M.

    2014-10-01

    Recent studies have confirmed the presence of buckminsterfullerene (C60) in different interstellar and circumstellar environments. However, several aspects regarding C60 in space are not yet well understood, such as the formation and excitation processes, and the connection between C60 and other carbonaceous compounds in the interstellar medium, in particular polycyclic aromatic hydrocarbons (PAHs). In this paper, we study several photodissociation regions (PDRs) where C60 and PAHs are detected and the local physical conditions are reasonably well constrained to provide observational insights into these questions. C60 is found to emit in PDRs where the dust is cool (Td = 20-40 K) and even in PDRs with cool stars. These results exclude the possibility for C60 to be locked in grains at thermal equilibrium in these environments. We observe that PAH and C60 emission are spatially uncorrelated and that C60 is present in PDRs where the physical conditions (in terms of radiation field and hydrogen density) allow for full dehydrogenation of PAHs, with the exception of Ced 201. We also find trends indicative of an increase in C60 abundance within individual PDRs, but these trends are not universal. These results support models where the dehydrogenation of carbonaceous species is the first step toward C60 formation. However, this is not the only parameter involved and C60 formation is likely affected by shocks and PDR age.

  15. Molecule-specific interactions of diatomic adsorbates at metal-liquid interfaces

    PubMed Central

    Kraack, Jan Philip; Kaech, Andres; Hamm, Peter

    2017-01-01

    Ultrafast vibrational dynamics of small molecules on platinum (Pt) layers in water are investigated using 2D attenuated total reflectance IR spectroscopy. Isotope combinations of carbon monoxide and cyanide are used to elucidate inter-adsorbate and substrate-adsorbate interactions. Despite observed cross-peaks in the CO spectra, we conclude that the molecules are not vibrationally coupled. Rather, strong substrate-adsorbate interactions evoke rapid (∼2 ps) vibrational relaxation from the adsorbate into the Pt layer, leading to thermal cross-peaks. In the case of CN, vibrational relaxation is significantly slower (∼10 ps) and dominated by adsorbate-solvent interactions, while the coupling to the substrate is negligible. PMID:28396878

  16. Reversible switching among three adsorbate configurations in a single [2.2]paracyclophane-based molecule.

    PubMed

    Silien, C; Liu, N; Ho, W; Maddox, J B; Mukamel, S; Liu, B; Bazan, G C

    2008-01-01

    Single 4,7,12,15-tetrakis(4'-dimethylaminostyryl)[2.2]paracyclophane molecules adsorb on NiAl(110) in different configurations. When the symmetry axes of the molecules are properly oriented with respect to the surface lattice, three adsorbate states of different conductance can be reversibly induced and directly imaged with a scanning tunneling microscope. Couplings between tunneling electrons and adsorbate vibrational and electronic states are primarily responsible for the transformation. However, change from low to high conductance configuration can also be triggered by electric field in the junction.

  17. Solubility Characteristics of PCBM and C60.

    PubMed

    Boucher, David; Howell, Jason

    2016-11-10

    Empirical data indicate that several good solvents for C60 and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) have substantial polar and hydrogen-bonding components, which are not intrinsic to the structure of the C60 and PCBM molecules themselves. Functional solubility parameter (FSP) and convex solubility parameter (CSP) computations are performed on C60 and PCBM using solubility data available in the literature. The CSP and FSP results are compared to previously reported Hansen solubility parameters (HSPs) and to the parameters calculated using additive functional group contribution methods. The CSP and FSP methods confirm the anomalously large polar and hydrogen-bonding parameters, δP and δH, obtained experimentally for C60 and PCBM. This behavior, which is quite irregular given the structure of the molecules, is due to the fact that several good solvents have high δP and δH values. Thus, these irregularities are highlighted by the CSP and FSP calculations. Additional contradictory solubility characteristics are disclosed by comparing the experimental solubility parameters to a linear solvation energy relationship (LSER) model, additive functional group calculations, and COSMO-RS computations. The FSP solubility function strongly suggests that the solubility parameters do not accurately represent the cohesive energy density properties of C60 and PCBM, as intended, but rather they manifest the properties of the solvents, e.g., high δP and δH values, that are necessary to accommodate these molecules in the liquid phase.

  18. A Molecular Dynamics Simulation of C60-C60 Collision

    NASA Astrophysics Data System (ADS)

    Liu, Lei; Chen, Kaitai; Li, Yufen

    1993-12-01

    The formation process of C120-complex in C60-C60 collision has been clearly demonstrated by a molecular dynamics simulation. The complex, with a peanut-shell-like structure, is in a quite stable dynamical state. The results are consistent with recent observations.

  19. Substrate-mediated interactions and intermolecular forces between molecules adsorbed on surfaces.

    PubMed

    Sykes, E Charles H; Han, Patrick; Kandel, S Alex; Kelly, Kevin F; McCarty, Gregory S; Weiss, Paul S

    2003-12-01

    Adsorbate interactions and reactions on metal surfaces have been investigated using scanning tunneling microscopy. The manners in which adsorbates perturb the surface electronic structure in their vicinity are discussed. The effects these perturbations have on other molecules are shown to be important in overlayer growth. Interactions of molecules with surface steps are addressed, and each molecule's electron affinity is shown to dictate its adsorption sites at step edges. Standing waves emanating from steps are demonstrated to effect transient molecular adsorption up to 40 A away from the step edge. Halobenzene derivatives are used to demonstrate how the surface is important in aligning reactive intermediates.

  20. Relaxation dynamics of surface-adsorbed water molecules in nanoporous silica probed by terahertz spectroscopy

    NASA Astrophysics Data System (ADS)

    Huang, Yu-Ru; Liu, Kao-Hsiang; Mou, Chung-Yuan; Sun, Chi-Kuang

    2015-08-01

    Relaxation dynamics of an exclusively adsorbed water molecule in mesoporous silica MCM-41-S was studied by using terahertz spectroscopy. With the temperature controlled from 0 to 50 °C, we observed strongly frequency- and temperature-dependent dielectric relaxation responses, implying that, unlike ice, surface-adsorbed water molecules retained flourishing picosecond dynamics. Based on the Debye relaxation model, a relaxation time constant was found to increase from 1.77 to 4.83 ps when the water molecule was cooled from 50 to 0 °C. An activation energy of ˜15 kJ/mol, which was in close agreement with a hydrogen-bonding energy, was further extracted from the Arrhenius analysis. Combined with previous molecular dynamics simulations, our results indicate that the reorientation relaxation originated from the "flip-flop" rotation of a three hydrogen-bonded surface-adsorbed water molecule.

  1. Growth of C 60 films on silicon surfaces

    NASA Astrophysics Data System (ADS)

    Chen, Dong; Sarid, Dror

    1994-10-01

    The growth of crystalline C 60 films on Si(111) and Si (100) surfaces has been studied using scanning tunneling microscopy and atomic force microscopy. It is found that the films on these two silicon substrates, which consist of both partially ordered monolayer and crystalline islands, differ in their morphologies. The results are explained in terms of the relative strength of interaction of the first monolayer of C 60 molecules with the silicon substrate and the C 60 islands above it. Annealing the samples to elevated temperatures causes the C 60 islands to evaporate, leaving a full layer of C 60 molecules capped on the substrate.

  2. Laser electrospray mass spectrometry of adsorbed molecules at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Brady, John J.; Judge, Elizabeth J.; Simon, Kuriakose; Levis, Robert J.

    2010-02-01

    Atmospheric pressure mass analysis of solid phase biomolecules is performed using laser electrospray mass spectrometry (LEMS). A non-resonant femtosecond duration laser pulse vaporizes native samples at atmospheric pressure for subsequent electrospray ionization and transfer into a mass spectrometer. LEMS was used to detect a complex molecule (irinotecan HCl), a complex mixture (cold medicine formulation with active ingredients: acetaminophen, dextromethorphan HBr and doxylamine succinate), and a biological building block (deoxyguanosine) deposited on steel surfaces without a matrix molecule.

  3. Molecular Dynamics Simulation of Reflected Gas Molecules on Water Adsorbed Surface

    NASA Astrophysics Data System (ADS)

    Takeuchi, Hideki; Yamamoto, Kyoji; Hyakutake, Toru

    2008-12-01

    The Couette flow of a rarefied argon gas between two platinum walls is considered to investigate the characteristics of the reflected gas molecule at a physically adsorbed surface by H2O molecules. The analysis is based on the molecular dynamics (MD) method for the interaction of gas molecules with the wall surface together with the direct simulation Monte-Carlo (DSMC) method for the motion of gas molecule. The accommodation coefficients are obtained. The flow velocity distribution between two walls and the velocity distribution function of the reflected molecule are also obtained. It is found that the Maxwell type reflection condition describes the distribution function of the reflected molecules well.

  4. Isomerization of C60 fullerenes

    NASA Astrophysics Data System (ADS)

    Yi, Jae-Yel; Bernholc, J.

    1992-06-01

    Car-Parrinello calculations show that the transformation between C60 isomers involves barriers in excess of 5 eV, although the energetic difference between the buckyball and the next lowest isomer is only 1.6 eV. C60 isomerization thus requires high temperatures and long annealing times.

  5. Unconventional superconductivity induced in Nb films by adsorbed chiral molecules

    NASA Astrophysics Data System (ADS)

    Alpern, H.; Katzir, E.; Yochelis, S.; Katz, N.; Paltiel, Y.; Millo, O.

    2016-11-01

    Motivated by recent observations of chiral-induced magnetization and spin-selective transport we studied the effect of chiral molecules on conventional BCS superconductors. By applying scanning tunneling spectroscopy, we demonstrate that the singlet-pairing s-wave order parameter of Nb is significantly altered upon adsorption of chiral polyalanine alpha-helix molecules on its surface. The tunneling spectra exhibit zero-bias conductance peaks embedded inside gaps or gap-like features, suggesting the emergence of unconventional triplet-pairing components with either d-wave or p-wave symmetry at the Nb organic-molecules interface, as corroborated by simulations. These results may open a way for realizing simple superconducting spintronics devices.

  6. C60 in Reflection Nebulae

    NASA Astrophysics Data System (ADS)

    Sellgren, Kris; Werner, Michael W.; Ingalls, James G.; Smith, J. D. T.; Carleton, T. M.; Joblin, Christine

    2010-10-01

    The fullerene C60 has four infrared-active vibrational transitions at 7.0, 8.5, 17.4, and 18.9 μm. We have previously observed emission features at 17.4 and 18.9 μm in the reflection nebula NGC 7023 and demonstrated spatial correlations suggestive of a common origin. We now confirm our earlier identification of these features with C60 by detecting a third emission feature at 7.04 ± 0.05 μm in NGC 7023. We also report the detection of these three C60 features in the reflection nebula NGC 2023. Our spectroscopic mapping of NGC 7023 shows that the 18.9 μm C60 feature peaks on the central star and that the 16.4 μm emission feature due to polycyclic aromatic hydrocarbons peaks between the star and a nearby photodissociation front. The observed features in NGC 7023 are consistent with emission from UV-excited gas-phase C60. We find that 0.1%-0.6% of interstellar carbon is in C60; this abundance is consistent with those from previous upper limits and possible fullerene detections in the interstellar medium (ISM). This is the first firm detection of neutral C60 in the ISM.

  7. 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.

  8. Transient magnetization of core excited organic molecules adsorbed on graphene

    NASA Astrophysics Data System (ADS)

    Ravikumar, Abhilash; Baby, Anu; Lin, He; Brivio, Gian Paolo; Fratesi, Guido

    This work presents a density functional theory based computational investigation of electronic and magnetic properties of physisorbed and chemisorbed organic molecules on graphene in the ground state and core excited one at low molecular coverage. For physisorbed molecules, where the interaction with graphene is dominated by van der Waals forces and the system is non-magnetic in the ground state, it is found that the valence electrons relax towards a spin polarized configuration upon excitation of a core-level electron. The magnetism depends on efficient electron transfer from graphene on the femtosecond time scale. On the contrary, when graphene is covalently functionalized, the system is magnetic in the ground state presenting two spin dependent mid gap states localized around the adsorption site. At variance with the physisorbed case upon core-level excitation, the LUMO of the molecule and the mid gap states of graphene hybridize and the relaxed valence shell is not magnetic anymore. This project has received funding from the European Union Seventh Framework Programme under grant agreement n∘ 607232 [THINFACE].

  9. Comparative Computational Study of Interaction of C60-Fullerene and Tris-Malonyl-C60-Fullerene Isomers with Lipid Bilayer: Relation to Their Antioxidant Effect

    PubMed Central

    Bozdaganyan, Marine E.; Orekhov, Philipp S.; Shaytan, Alexey K.; Shaitan, Konstantin V.

    2014-01-01

    Oxidative stress induced by excessive production of reactive oxygen species (ROS) has been implicated in the etiology of many human diseases. It has been reported that fullerenes and some of their derivatives–carboxyfullerenes–exhibits a strong free radical scavenging capacity. The permeation of C60-fullerene and its amphiphilic derivatives–C3-tris-malonic-C60-fullerene (C3) and D3-tris-malonyl-C60-fullerene (D3)–through a lipid bilayer mimicking the eukaryotic cell membrane was studied using molecular dynamics (MD) simulations. The free energy profiles along the normal to the bilayer composed of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) for C60, C3 and D3 were calculated. We found that C60 molecules alone or in clusters spontaneously translocate to the hydrophobic core of the membrane and stay inside the bilayer during the whole period of simulation time. The incorporation of cluster of fullerenes inside the bilayer changes properties of the bilayer and leads to its deformation. In simulations of the tris-malonic fullerenes we discovered that both isomers, C3 and D3, adsorb at the surface of the bilayer but only C3 tends to be buried in the area of the lipid headgroups forming hydrophobic contacts with the lipid tails. We hypothesize that such position has implications for ROS scavenging mechanism in the specific cell compartments. PMID:25019215

  10. Comparative computational study of interaction of C60-fullerene and tris-malonyl-C60-fullerene isomers with lipid bilayer: relation to their antioxidant effect.

    PubMed

    Bozdaganyan, Marine E; Orekhov, Philipp S; Shaytan, Alexey K; Shaitan, Konstantin V

    2014-01-01

    Oxidative stress induced by excessive production of reactive oxygen species (ROS) has been implicated in the etiology of many human diseases. It has been reported that fullerenes and some of their derivatives-carboxyfullerenes-exhibits a strong free radical scavenging capacity. The permeation of C60-fullerene and its amphiphilic derivatives-C3-tris-malonic-C60-fullerene (C3) and D3-tris-malonyl-C60-fullerene (D3)-through a lipid bilayer mimicking the eukaryotic cell membrane was studied using molecular dynamics (MD) simulations. The free energy profiles along the normal to the bilayer composed of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) for C60, C3 and D3 were calculated. We found that C60 molecules alone or in clusters spontaneously translocate to the hydrophobic core of the membrane and stay inside the bilayer during the whole period of simulation time. The incorporation of cluster of fullerenes inside the bilayer changes properties of the bilayer and leads to its deformation. In simulations of the tris-malonic fullerenes we discovered that both isomers, C3 and D3, adsorb at the surface of the bilayer but only C3 tends to be buried in the area of the lipid headgroups forming hydrophobic contacts with the lipid tails. We hypothesize that such position has implications for ROS scavenging mechanism in the specific cell compartments.

  11. Rotational Spectromicroscopy: Imaging the Orbital Interaction between Molecular Hydrogen and an Adsorbed Molecule

    NASA Astrophysics Data System (ADS)

    Li, Shaowei; Yuan, Dingwang; Yu, Arthur; Czap, Gregory; Wu, Ruqian; Ho, W.

    2015-05-01

    A hydrogen molecule can diffuse freely on the surface and be trapped above an adsorbed molecule within the junction of a scanning tunneling microscope. The trapped dihydrogen exhibits the properties of a free rotor. Here we show that the intermolecular interaction between dihydrogen and Mg-porphyrin (MgP) can be visualized by imaging j =0 to 2 rotational excitation of dihydrogen. The interaction leads to a weakened H-H bond and modest electron donation from the dihydrogen to the lowest unoccupied molecular orbital of MgP, a process similarly observed for the interaction between dihydrogen and an adsorbed Au atom.

  12. Resonant electron scattering by molecules adsorbed on a surface: N2-Ag system

    NASA Astrophysics Data System (ADS)

    Teillet-Billy, D.; Djamo, V.; Gauyacq, J. P.

    1992-05-01

    A model study of resonant electron scattering by static molecules adsorbed on a metal surface is presented, using the recently developed coupled angular mode (CAM) method. It is applied to the case of N2 molecules adsorbed on an Ag surface. The N2-2πg resonance characteristics (energy position and width) are determined and shown to be modified by the presence of the surface in qualitative agreement with the experimental results of Demuth et al. [Phys. Rev. Lett. 47 (1981) 1166].

  13. Vibrational properties of water molecules adsorbed in different zeolitic frameworks

    NASA Astrophysics Data System (ADS)

    Crupi, V.; Longo, F.; Majolino, D.; Venuti, V.

    2006-04-01

    The perturbation of water 'sorbed' in samples of zeolites of different structural type, genesis, and cation composition (K-, Na-, Mg- and Ca-rich zeolites), namely the CHA framework of a synthetic K-chabazite, the LTA framework of synthetic Na-A and Mg50-A zeolites, and the NAT framework of a natural scolecite, has been studied by FTIR-ATR spectroscopy, in the -10 to +80 °C temperature range. The aim was to show how differences in the chemical composition and/or in the topology of the zeolite framework and, in particular, the possibility for the guest water molecules to develop guest-guest and/or host-guest interactions, lead to substantial differences in their vibrational dynamical properties. The spectra, collected in the O-H stretching and H2O bending mode regions, are complex, with multiple bands being observed. As far as water in the CHA and LTA frameworks is concerned, whose behaviour is governed by the balance of water-water, water-framework and water-extra-framework cations interactions, the assignment of the resolved components of the O-H stretching band has been discussed by fitting the band shapes into individual components attributed to H2O molecules engaged in different degrees of hydrogen bonding. A detailed quantitative picture of the connectivity pattern of water, as a function of temperature and according to the chemical and topological properties of the environment, is furnished. The H2O bending vibrational bands give additional information that perfectly agrees with the results obtained from the analysis of the O-H stretching spectral region. In the case of scolecite, a small-pored zeolite where water-water interactions are eliminated, the increased complexity observed in the infrared spectra in the O-H stretching and H2O bending regions was explained as due to the hydrogen bonding between the water molecules and the network, and also with the extra-framework cation. Furthermore, these observations have been correlated with the different

  14. Photophysics of C60 Colloids

    DTIC Science & Technology

    2012-11-28

    illumination," Fullerenes, Nanotubes and Carbon Nanostructures 9(3), 351 - 361 (2001). 46. A. Kost, L. W. Tutt, M. B. Klein, T. K. Dougherty, and W. E...properties of singlewall carbon nanotubes ," Optics Communications 174(1-4), 271-275 (2000). 130. J. Williams, "Oceanographic Instrumentation," in...of C60 and carbon black suspensions (CBS). C60 in molecular form is known to exhibit strong reverse saturable absorption (RSA) and it is posited that

  15. Photoacoustic spectroscopy of surface adsorbed molecules using a nanostructured coupled resonator array

    NASA Astrophysics Data System (ADS)

    Lee, Dongkyu; Kim, Seonghwan; Van Neste, C. W.; Lee, Moonchan; Jeon, Sangmin; Thundat, Thomas

    2014-01-01

    A rapid method of obtaining photoacoustic spectroscopic signals for trace amounts of surface adsorbed molecules using a nanostructured coupled resonator array is described. Explosive molecules adsorbed on a nanoporous anodic aluminum oxide cantilever, which has hexagonally ordered nanowells with diameters and well-to-well distances of 35 nm and 100 nm, respectively, are excited using pulsed infrared (IR) light with a frequency matching the common mode resonance frequency of the coupled resonator. The common mode resonance amplitudes of the coupled resonator as a function of illuminating IR wavelength present a photoacoustic IR absorption spectrum representing the chemical signatures of the adsorbed explosive molecules. In addition, the mass of the adsorbed molecules as an orthogonal signal for quantitative analysis is determined by measuring the variation of the localized, individual mode resonance frequency of a cantilever on the array. The limit of detection of the ternary mixture of explosive molecules (1:1:1 of trinitrotoluene (TNT), cyclotrimethylene trinitramine (RDX) and pentaerythritol tetranitrate (PETN)) is estimated to be ˜100 ng cm-2. These multi-modal signals enable us to perform quantitative and rapid chemical sensing and analysis in ambient conditions.

  16. Dynamics of Molecules Adsorbed in Zeolitic Systems: Neutron Scattering and MD Simulation Studies

    NASA Astrophysics Data System (ADS)

    Mitra, S.; Sharma, V. K.; Mukhopadhyay, R.

    2011-07-01

    Zeolites represent a class of technologically important materials because of their characteristic properties of molecular sieving and catalysis, which makes them indispensable in the petroleum industries. While the catalytic properties depend upon many factors, a major role is played by the dynamics of hydrocarbon gases. In order to be able to tailor make these materials for use in industry for catalytic and sieving purposes, it is important to understand the dynamical properties of the guest molecules adsorbed in the zeolitic materials. It is of interest to study the effects of size and shape of guest molecules and also the host zeolitic structure, governing the diffusion mechanism of the adsorbed species. Here we report the results of Quasielastic Neutron Scattering (QENS) and classical molecular dynamics (MD) simulation studies of two hydrocarbons namely acetylene and propylene adsorbed in two structurally different zeolites Na-Y and ZSM-5.

  17. Cooperative Assembly of Magic Number C60-Au Complexes

    NASA Astrophysics Data System (ADS)

    Xie, Yang-Chun; Tang, Lin; Guo, Quanmin

    2013-11-01

    We report the assembly of magic number (C60)m-(Au)n complexes on the Au(111) surface. These complexes have a unique structure consisting of a single atomic layer Au island wrapped by a self-selected number (seven, ten, or twelve) of C60 molecules. The smallest structure consisting of 7 C60 molecules and 19 Au atoms, stable up to 400 K, has a preferred orientation on the surface. We propose a globalized metal-organic coordination mechanism for the stability of the (C60)m-(Au)n complexes.

  18. Ionization energies of the C60 fullerene and its hydrogenated derivatives C60H18 and C60H36 determined by electron ionization

    NASA Astrophysics Data System (ADS)

    Pogulay, Andrey V.; Abzalimov, Rinat R.; Nasibullaev, Shamil'k.; Lobach, Anatoly S.; Drewello, Thomas; Vasil'Ev, Yury V.

    2004-04-01

    Modification of a method for processing positive ion ionization efficiency curves of polyatomic molecules, as developed earlier by Märk and coworkers, has been described. Based on the method, the first, second, and third ionization energies of C60 have been re-examined and found to be in excellent agreement with the most reliable literature data. The ionization energies for C60H18 and C60H36 have been measured for the first time and were established as 7.3+/-0.3 eV and 7.01+/-0.25 eV, respectively. Although the appearance energy of C60H362+ (18.7+/-0.2 eV) has been determined to be lower than that of C602+ (18.98+/-0.35 eV), the reverse scenario is true for the second ionization energies of C60H36 and C60.

  19. Vibrational excitation of adsorbed molecules by low-energy photon-emitted electrons: A dynamical model

    NASA Astrophysics Data System (ADS)

    González Ureña, A.; Telle, H. H.; Tornero, J.

    2013-01-01

    A simple, inelastic electron-scattering dynamical model is presented to account for vibrational excitation in molecular adsorbates. The basic two ingredients of the theoretical model are: (i) the conservation of the total angular momentum, and (ii) the requirement of a critical time to allow for the intra-molecular energy re-arrangement of the transient negative-ion complex. The model is applied to the vibrational excitation dynamics of molecules chemisorbed at sub-monolayer conditions on ordered metal surfaces. This was exemplified for Acrylonitrile adsorbed on Cu(1 0 0), whose vibrational excitation was studied via energy loss spectra of low-energy two-photon photoemission (2PPE) electrons, and for ammonia (NH3 and ND3) adsorbed on Cu(1 0 0), being probed in a STM experiment. Fits of the model to the data allowed for deducing the energy threshold of the vibrational excitation of the Cdbnd C and Ctbnd N bonds of the ACN adsorbate molecules, and the threshold for the symmetric ν1-stretch mode excitation of adsorbed NH3/ND3. Also, information about the temporal dynamics underlying the inelastic electron scattering was gained.

  20. Single Photon Thermal Ionization of C60

    NASA Astrophysics Data System (ADS)

    Hansen, Klavs; Richter, Robert; Alagia, Michele; Stranges, Stefano; Schio, Luca; Salén, Peter; Yatsyna, Vasyl; Feifel, Raimund; Zhaunerchyk, Vitali

    2017-03-01

    We report on experiments which show that C60 can ionize in an indirect, quasithermal boiloff process after absorption of a single photon. The process involves a large number of incoherently excited valence electrons and yields electron spectra with a Boltzmann distribution with temperatures exceeding 104 K . It is expected to be present for other molecules and clusters with a comparatively large number of valence electrons. The astrophysical consequences are briefly discussed.

  1. Removal of sulfur-containing organic molecules adsorbed on inorganic supports by Rhodococcus Rhodochrous spp.

    PubMed

    Carvajal, P; Dinamarca, M Alejandro; Baeza, P; Camú, E; Ojeda, J

    2017-02-01

    To remove dibenzothiophene (DBT) and 4,6-dimethyl-dibenzothiophene (4,6-DMDBT) adsorbed on alumina, silica and sepiolite through biodesulfurization (BDS) using Rhodococcus Rhodochrous spp., that selectively reduce sulfur molecules without generating of gaseous pollutants. The adsorption of DBT and 4,6-DMDBT was affected by the properties of the supports, including particle size and the presence of surface acidic groups. The highest adsorption of both sulfur-containing organic molecules used particle sizes of 0.43-0.063 mm. The highest percentage removal was with sepiolite (80 % for DBT and 56 % for 4,6-DMDBT) and silica (71 % for DBT and 37 % for 4,6-DMDBT). This is attributed to the close interaction between these supports and the bacteria. Biodesulfurization is effective for removing the sulfur-containing organic molecules adsorbed on inorganic materials and avoids the generation of gaseous pollutants.

  2. Ion bombardment of C60 films

    NASA Astrophysics Data System (ADS)

    Hobday, Steven; Smith, Roger; Gibson, Ursula; Richter, Asta

    The interaction of energetic ions with C60 films in the energy range 300-1000 eV is studied by computer simulation. It is found that the films can be subjected to much more surface damage than would be expected in other forms of carbon. Ejection of particles from the surface takes place in two ways. First, individual carbon atoms can be displaced from the lattice by ballistic collision processes. These are relatively few in number and the phenomenon occurs over a short timescale, of less than 0.5 ps. As the collision cascade develops, energy deposited in the surface region can be transferred to surface C60 molecules in sufficient quantity for some of these to be desorbed. This phenomena occurs over the order of a few picoseconds and can result in the loss of up to five C60's from the surface. The damage induced to the lattice causes C60's to be linked together in the form of polymerised chains. There is also evidence of the formation of 2- and 4-fold co-ordinated bonds in the lattice and transition to amorphous carbon.

  3. Structure, Dynamics, and Thermodynamics of Small Molecules Adsorbed in Zeolite Micropores: Simulation and Statistical Mechanics.

    NASA Astrophysics Data System (ADS)

    van Tassel, Paul Robert

    1993-01-01

    This thesis describes a fully detailed molecular simulation and modeling effort aimed at understanding the fundamentals of adsorption and diffusion of small molecules in zeolite micropores. The primary emphasis is on determining the relationship between the structure and chemistry of the zeolite adsorbent and the structure, dynamics, and thermodynamics of the adsorbed phase. Further emphasis is on developing simple, predictive models of zeolite adsorption and diffusion. We begin by presenting a Monte Carlo simulation of single component adsorption of xenon, methane, and argon in zeolite NaA. The form of the adsorbate density distribution indicates the presence of discrete adsorption sites which arrange in polyhedra whose geometry depends on the number and position of zeolite framework ions. Isotherm plateaus are attributed to either (i) a low energy adsorbate configuration or (ii) the saturation of polyhedral sites. Viewing the adsorbed phase as an ordered arrangement differs from the conventional delocalized model, yet it helps explain certain experimental observations. Next, a study of binary mixtures of small molecules in zeolite NaA using the Monte Carlo method is presented. The mixing in the pore is determined to be highly nonideal by comparison to a simple pore volume filling model. Strong selectivity for a more polarizable molecule (xenon) is observed only at low pore loading. At higher pore loading, a smaller, less polarizable molecule (argon) adsorbs selectively at a significantly lower pressure than predicted by the model. This enhanced selectivity is due to the ability of the smaller molecule to pack more efficiently inside of the pore. Finally, we present two simple lattice models whose forms are arrived at following careful consideration of simulation results. The first describes the adsorption of small molecules in a zeolite. A polyhedral lattice is postulated whose neighboring sites interact energetically and entropically. The second model describes

  4. CROSS-DISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY: Two Possible Configurations for Silver-C60-Silver Molecular Devices and Their Conductance Characteristics

    NASA Astrophysics Data System (ADS)

    Tian, Guang-Jun; Su, Wen-Yong

    2009-06-01

    Coherent electronic transport properties of silver-C60-silver molecular junctions in different configurations are studied using hybrid density function theory. The experimentally measured current flows of C60 molecules adsorbed on the silver surface are well reproduced by theoretical calculations. It is found that the current-voltage characteristics of the molecular junctions depend strongly on the configurations of the junctions. Transmission spectra combined with density of states can help us to understand in depth the transport properties. Different kinds of electrode construction are also discussed. With the help of the calculation, two possible configurations of silver-C60-silver molecular junctions are suggested.

  5. Equation of state for fullerite C60

    NASA Astrophysics Data System (ADS)

    Rekhviashvili, S. Sh.

    2017-04-01

    A new equation of state for fullerite C60 is derived in the framework of the quantum-statistical method. This equation includes two Grüneisen parameters responsible for vibration-rotational and intramolecular contributions of fullerene molecules, which are represented in the form of isotropic quantum oscillators. The intramolecular vibrations of carbon atoms are described by the Debye heat capacity theory, and the cold contribution to the free energy is calculated using the Lennard-Jones pair potential for fullerene molecules. The theory is in a very good agreement with the experiment.

  6. 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

  7. Adlayers of C60-C60 and C60-C70 fullerene dimers formed on au(111) in benzene solutions studied by STM and LEED.

    PubMed

    Matsumoto, Masashi; Inukai, Junji; Tsutsumi, Eishi; Yoshimoto, Soichiro; Itaya, Kingo; Ito, Osamu; Fujiwara, Koichi; Murata, Michihisa; Murata, Yasujiro; Komatsu, Koichi

    2004-02-17

    Scanning tunneling microscopy (STM) and low-energy electron diffraction were used to reveal the structures of ordered adlayers of [2+2]-type C60-C60 fullerene dimer (C120) and C60-C70 cross-dimer (C130) formed on Au(111) by immersingit in abenzene solution containing C120 or C130 molecules. High-resolution STM images clearly showed the packing arrangements and the electronic structures of C120 and C130 on the Au(111) surface in ultrahigh vacuum. The (2 square root3 x 4square root3)R30 degrees, (2square root3 x 5square root3)R30 degrees, and (7 x 7) structures were found for the C120 adlayer on the Au(111) surface, whereas C130 molecules were closely packed on the surface. Each C60 or C70 monomer cage was discerned in the STM image of a C130 molecule.

  8. Entanglement of Spin States in 15N@C60

    NASA Astrophysics Data System (ADS)

    Scherer, W.; Weidinger, A.; Mehring, M.

    2004-09-01

    The endohedral fullerene 15N@C60 comprises an electron spin S = 3/2 coupled to a nuclear spin I = 1/2 and is therefore ideally suited for experimental testing of basic properties of quantum mechanics. We will show that the 15N@C60 molecule represents a multi qubit system where different kinds of entangled states can be generated.

  9. Rod-like cyanophenyl probe molecules nanoconfined to oxide particles: Density of adsorbed surface species

    NASA Astrophysics Data System (ADS)

    Frunza, Stefan; Frunza, Ligia; Ganea, Constantin Paul; Zgura, Irina; Brás, Ana Rita; Schönhals, Andreas

    2016-02-01

    Surface layers have already been observed by broadband dielectric spectroscopy for composite systems formed by adsorption of rod-like cyanophenyl derivates as probe molecules on the surface of oxide particles. In this work, features of the surface layer are reported; samples with different amounts of the probe molecules adsorbed onto oxide (nano) particles were prepared in order to study their interactions with the surface. Thermogravimetric analysis (TGA) was applied to analyze the amount of loaded probe molecules. The density of the surface species ns was introduced and its values were estimated from quantitative Fourier transform infrared spectroscopy (FTIR) coupled with TGA. This parameter allows discriminating the composites into several groups assuming a similar interaction of the probe molecules with the hosts of a given group. An influence factor H is further proposed as the ratio of the number of molecules in the surface layer showing a glassy dynamics and the number of molecules adsorbed tightly on the surface of the support: It was found for aerosil composites and used for calculating the maximum filling degree of partially filled silica MCM-41 composites showing only one dielectric process characteristic for glass-forming liquids and a bulk behavior for higher filling degrees.

  10. Stability, structural and electronic properties of benzene molecule adsorbed on free standing Au layer

    SciTech Connect

    Katoch, Neha Kapoor, Pooja; Sharma, Munish; Ahluwalia, P. K.; Kumar, Ashok

    2016-05-23

    We report stability and electronic properties of benzene molecule adsorbed on the Au atomic layer within the framework of density function theory (DFT). Horizontal configuration of benzene on the top site of Au monolayer prefers energetically over other studied configurations. On the adsorption of benzene, the ballistic conductance of Au monolayer is found to decrease from 4G{sub 0} to 2G{sub 0} suggesting its applications for the fabrications of organic sensor devices based on the Au atomic layers.

  11. Stability, structural and electronic properties of benzene molecule adsorbed on free standing Au layer

    NASA Astrophysics Data System (ADS)

    Katoch, Neha; Kapoor, Pooja; Sharma, Munish; Kumar, Ashok; Ahluwalia, P. K.

    2016-05-01

    We report stability and electronic properties of benzene molecule adsorbed on the Au atomic layer within the framework of density function theory (DFT). Horizontal configuration of benzene on the top site of Au monolayer prefers energetically over other studied configurations. On the adsorption of benzene, the ballistic conductance of Au monolayer is found to decrease from 4G0 to 2G0 suggesting its applications for the fabrications of organic sensor devices based on the Au atomic layers.

  12. Morphological phase diagrams of C60 and C70 films on graphite

    NASA Astrophysics Data System (ADS)

    Sato, Kazuma; Tanaka, Tomoyasu; Akaike, Kouki; Kanai, Kaname

    2017-10-01

    The morphologies of C60 and C70 fullerene films vacuum-deposited onto graphite at various deposition rates and grown at several temperatures were investigated using atomic force microscopy. These fullerene films on graphite are model systems of physisorption of organic molecules that likely exhibit little chemical interaction with the graphite's surface. The morphologies of C60 and C70 films grown on graphite can be understood well from growth models previously reported. Comparison of the morphological phase diagrams obtained for C60 and C70 indicate that the diffusion properties of the adsorbed molecule are key in determining the morphology of the obtained film. The low diffusion rate of C70 resulted in various film morphologies for all deposition conditions tested. Also, the obtained phase diagrams can be understood by the results of fractal dimension analysis on the C60 and C70 islands. The fundamental understanding of film growth obtained using these ideal physisorption systems will aid in understanding film growth by other molecular adsorption systems.

  13. Formation and decay of C - 60 following free electron capture by C60

    NASA Astrophysics Data System (ADS)

    Matejčik, Štefan; Märk, Tilmann D.; Španěl, Patrik; Smith, David; Jaffke, Thomas; Illenberger, Eugen

    1995-02-01

    The results of a detailed crossed electron/molecular beam study of electron attachment to C60 molecules and electron detachment from C-60 over the range of electron energies from near zero to about 15 eV are described. It is shown by comparing the experimental data for the attachment cross sections (normalized to the absolute thermal cross sections determined using the flowing afterglow/Langmuir probe apparatus) with quantum calculations that attachment occurs at low energies in the p-wave channel, and in the d- and f-wave channels (and probably higher-order partial waves) at the higher electron energies. At electron energies above 7 eV, thermal detachment of electrons from the hot C-60 negative ions is seen to occur, and the unimolecular rate coefficients for detachment, kd, have been determined as a function of the energy of the attaching electron. Hence, by relating kd to the derived temperature of the hot C-60 ions, the electron detachment energy, Ed, has been determined as 2.6 eV, which is close to the electron affinity of C60 as measured by photodetachment from cold C-60 ions. Additionally, by combining the measured attachment rate coefficients, ka, from the previous flowing afterglow/Langmuir probe study with the kd data determined in this study, equilibrium constants for the detachment/attachment reactions have been obtained which are reconciled with those calculated using total partition functions. An important conclusion to be drawn from all these studies is that C60 very efficiently captures electrons over the wide electron energy range from about 0.2 eV to around 15 eV and retains them if the energy released in the electron capture process can be removed before thermal detachment can occur.

  14. SERS of Gold/C 60 (/C 70) nano-clusters deposited on floppy disk and hard disk

    NASA Astrophysics Data System (ADS)

    Luo, Zhixun; Fang, Yan

    2006-01-01

    It is important to apply the surface enhanced Raman scattering (SERS) spectra to study the interfacial properties of films and the adsorption behavior of molecules on substrates. In this paper, SERS spectra of good quality of gold/C 60 (/C 70) nano-clusters deposited on floppy disk and hard disk were reported with the pyridine as a kind of solvent intermediate. The floppy disk or hard disk, as a new and effective substrate for SERS, provides a plank for C 60/C 70 molecules to adsorb on the gold nano-particles. The number of vibrational modes was greatly increased, especially some modes that were forbidden in Raman spectrum, appeared and even split as prediction of group theory. The enhancement factor is estimated to over 10 6. It provides convenience for probing the C 60/C 70 vibrational structure and the physical properties with the high sensitivity, as well as the adsorption behavior, the interaction of fullerene with gold surface and the SERS mechanism of molecules adsorbed on substrates. What's more, the SERS sensitivity of the magnetism is demonstrated by comparing the SERS of gold/C 60 (/C 70) nano-clusters deposited on floppy disk and hard disk.

  15. Rotational superstructure in van der Waals heterostructure of self-assembled C60 monolayer on the WSe2 surface.

    PubMed

    Santos, Elton J G; Scullion, Declan; Chu, Ximo S; Li, Duo O; Guisinger, Nathan P; Wang, Qing Hua

    2017-09-14

    Hybrid van der Waals (vdW) heterostructures composed of two-dimensional (2D) layered materials and self-assembled organic molecules are promising systems for electronic and optoelectronic applications with enhanced properties and performance. Control of molecular assembly is therefore paramount to fundamentally understand the nucleation, ordering, alignment, and electronic interaction of organic molecules with 2D materials. Here, we report the formation and detailed study of highly ordered, crystalline monolayers of C60 molecules self-assembled on the surface of WSe2 in well-ordered arrays with large grain sizes (∼5 μm). Using high-resolution scanning tunneling microscopy (STM), we observe a periodic 2 × 2 superstructure in the C60 monolayer and identify four distinct molecular appearances. Using vdW-corrected ab initio density functional theory (DFT) simulations, we determine that the interplay between vdW and Coulomb interactions as well as adsorbate-adsorbate and adsorbate-substrate interactions results in specific rotational arrangements of the molecules forming the superstructure. The orbital ordering through the relative positions of bonds in adjacent molecules creates a charge redistribution that links the molecule units in a long-range network. This rotational superstructure extends throughout the self-assembled monolayer and opens a pathway towards engineering aligned hybrid organic/inorganic vdW heterostructures with 2D layered materials in a precise and controlled way.

  16. Negative differential resistance in C60-based electronic devices.

    PubMed

    Zheng, Xiaohong; Lu, Wenchang; Abtew, Tesfaye A; Meunier, Vincent; Bernholc, Jerry

    2010-12-28

    Unlike single-C(60)-based devices, molecular assemblies based on two or more appropriately connected C(60) molecules have the potential to exhibit negative differential resistance (NDR). In this work, we evaluate electron transport properties of molecular devices built from two C(60) molecules connected by an alkane chain, using a nonequilibrium Green function technique implemented within the framework of density functional theory. We find that electronic conduction in these systems is mediated by the lowest unoccupied molecular orbitals (LUMOs) of C(60), as in the case of a single-C(60)-based device. However, as the positions of the LUMOs are pinned to the chemical potentials of their respective electrodes, their relative alignment shifts with applied bias and leads to a NDR at a very low bias. Furthermore, the position and magnitude of the NDR can be tuned by chemical modification of the C(60) molecules. The role of the attached molecules is to shift the LUMO position and break the symmetry between the forward and reverse currents. The NDR feature can also be controlled by changing the length of the alkane linker. The flexibility and richness of C(60)-based molecular electronics components point to a potentially promising route for the design of molecular devices and chemical sensors.

  17. Chemical effects on vibrational properties of adsorbed molecules on metal surfaces: Coverage dependence

    NASA Astrophysics Data System (ADS)

    Ueba, H.

    1987-10-01

    Vibrational properties of chemisorbed molecules on metal surfaces are studied with a focus on the coverage dependent chemical shift of the frequencies. Available experimental data of a CO adsorption on transition metal and noble metal surfaces are analyzed in the light of the coverage dependent back-donation into the 2 π* orbitals of chemisorbed CO molecules. The vibrational frequency ωCO of the intramolecular stretching mode exhibits a downward shift of varying magnitude, depending on the amount of back-donation into the 2 π* orbitals of the chemisorbed CO. On increasing the coverage θ, ωCO usually increases due to the dipole-dipole interaction. On Cu surfaces, however, the shifts are relatively small, or in some cases, negative. So far, this anomalous frequency shift with θ is understood as a result of competitive effect between the upward dipole Ωdip and the downward chemical shift Ωchem associated with back-donation. The purpose of this paper is to establish the possible origin of the downward frequency shift through the electronic properties of an incomplete monolayer of adsorbates. The adsorbate density of states ρa is calculated by means of the coherent potential approximation, in which the electron hopping between the adsorbates (band formation effect) and the depolarization effect due to the proximity of ionized adsorbed molecules are taken into account. The change of the occupied portion of ρa and ρa ( ɛF) at the Fermi level ɛF with increasing θ then manifests itself in the coverage dependent Ωchem not only due to the static back-donation, but also due to the dynamical charge fluctuation during vibrational excitation. It is found that in a weakly chemisorbed system, such as CO/Cu, the negative Ωchem amounts to Ωdip at low θ. Consequently the apparent total frequency shift remains almost constant. As the coverage increases, Ωchem becomes larger than Ωdip due to the band effect. It is also shown that the variation of the back

  18. Thermodynamic characteristics of the adsorption of organic molecules on modified MCM-41 adsorbents

    NASA Astrophysics Data System (ADS)

    Gus'kov, V. Yu.; Sukhareva, D. A.; Salikhova, G. R.; Karpov, S. I.; Kudasheva, F. Kh.; Roessner, F.; Borodina, E. V.

    2017-07-01

    The adsorption of a number of organic molecules on samples of MCM-41 adsorbent modified with dichloromethylphenylsilane and subsequently treated with sulfuric acid (MDCS) and N-trimethoxysilylpropyl- N, N, N-trimethylammonium chloride (MNM) is studied. Specific retention volumes equal to the Henry constant are determined by means of inverse gas chromatography at infinite dilution. The thermodynamic characteristics of adsorption, the dispersive and specific components of the Helmholtz energy of adsorption, and the increment of the methyl group to the heat of adsorption are calculated. It is shown that the grafting of aminosilane and phenylsilane groups enhances the forces of dispersion and reduces specific interactions. A greater drop in polarity is observed for MDCS than for MNM, due to the stronger polarity of amoinosilane; the enthalpy factor makes the main contribution to the adsorption of organic compounds on the investigated adsorbents. It is found that the MNM sample is capable of the irreversible adsorption of alcohols.

  19. Formation of Adsorbed Oxygen Radicals on Minerals at the Martian Surface and the Decomposition of Organic Molecules

    NASA Technical Reports Server (NTRS)

    Yen, A. S.; Kim, S. S.; Freeman, B. A.; Hecht, M. H.

    2000-01-01

    We present experimental evidence that superoxide ions form on mineral grains at the martian surface and show that these adsorbates can explain the unusual reactivity of the soil as well as the apparent absence of organic molecules.

  20. Formation of Adsorbed Oxygen Radicals on Minerals at the Martian Surface and the Decomposition of Organic Molecules

    NASA Technical Reports Server (NTRS)

    Yen, A. S.; Kim, S. S.; Freeman, B. A.; Hecht, M. H.

    2000-01-01

    We present experimental evidence that superoxide ions form on mineral grains at the martian surface and show that these adsorbates can explain the unusual reactivity of the soil as well as the apparent absence of organic molecules.

  1. Homeotropic orientation of a nematic liquid crystal by bent-core molecules adsorbed on its surface

    NASA Astrophysics Data System (ADS)

    Hwang, Jiyong; Yang, Seungbin; Lee, Hyojin; Kim, Jongyoon; Lee, Ji-Hoon; Kang, Shin-Woong; Choi, E.-Joon

    2015-06-01

    We reported the promotion of a homeotropic alignment of a nematic liquid crystal (NLC) by bent-core liquid-crystal (BLC) Molecules adsorbed its surface. The BLC was mixed at various concentrations with the NLC, and the mixtures were injected into an empty cell with a cell gap of 13 μm. Although the pure NLC showed a heterogeneous orientation, the BLC-NLC mixture was gradually transformed to a homeotropic alignment with increasing concentration of the BLC. We investigated the surface topography of the samples by using an atomic force microscopy (AFM) and found that the BLC molecules were segregated into a polyimide (PI) surface and formed protrusion domains with diameters of 50-100 nm. The BLC protrusions might promote the homeotropic orientation of the NLC molecules.

  2. Structure formation in adsorbed overlayers comprising functional cross-shaped molecules: A Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Kasperski, Adam; Nieckarz, Damian; Szabelski, Paweł

    2015-11-01

    Surface confined self-assembly of functional star-shaped organic molecules is a promising method to create nanoporous networks with tailorable structure and functions. In this work we use the Monte Carlo simulation method to demonstrate how the morphology of these supramolecular assemblies can be tuned by manipulating intrinsic parameters of the building blocks and modified by the presence of co-adsorbed metal atoms. To that purpose we study the 2D self-assembly of planar cruciform molecules modeled as collections of interconnected segments, some of which were activated to represent discrete interaction centers. We consider a few exemplary adsorbed systems in which the molecules with different size, aspect ratio and intramolecular distribution of active centers form superstructures stabilized by short-range segment-segment interactions or by metal-segment interactions. These two situations correspond to supramolecular assemblies sustained by, for example, hydrogen bonding and metal-organic ligand coordination, respectively. The simulated results show that proper encoding of intramolecular interactions into the cruciform building bricks allows for directing the self-assembly towards largely diversified structures ranging from nanoclusters to porous grids. The obtained findings can facilitate designing and optimization of molecular networks comprising cross-shaped units including functionalized porphyrins and phthalocyanines and they can be helpful in preliminary selection of these building blocks.

  3. 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.

  4. Rotational dynamics of endohedral C60 fullerene complexes

    NASA Astrophysics Data System (ADS)

    Hernández-Rojas, J.; Bretón, J.; Gomez Llorente, J. M.

    1997-11-01

    The structure of the rotational low-energy eigenvalue spectrum and eigenfunction of endohedral C60 fullerene complexes is investigated. The selected systems are Li+@C60, Na+@C60, CO@C60, and LiH@C60. The eigenvalue spectra may be classified basically into two types. Below some critical degree of anisotropy in the guest-cage interaction the spectrum looks rather simple, and similar to that of an effective diatomic molecule. For high enough anisotropic interactions, the low-energy eigenvalue spectrum is characterized by a double-band structure: a ground band localized around the fullerene hexagon centers, and an excited band embedded in a rotational quasi-continuum and localized at the unstable equilibrium regions around the fullerene pentagon centers. The cage rotation makes the transition from one type to the other much sharper type. Rotation dipole and Raman spectra are assigned in terms of these two types of structure in the eigenvalue spectrum.

  5. A model for the release of adsorbed molecules from the surfaces of airborne particulate matter based on liquid-phase desorption from amorphous carbon blacks.

    PubMed Central

    Risby, T H; Sehnert, S S; Jiang, L; Dhingra, B S

    1988-01-01

    The release of molecules adsorbed on the surfaces of amorphous carbon blacks has been studied using liquid-solid chromatography. Adsorbate molecules, adsorbents, and mobile phases were selected on the basis of their relevance as models for the release of toxic agents adsorbed on inhalable environmental particulate matter that originates from the incomplete combustion of organic materials. The presence of surface active groups on the carbon blacks has been shown to adsorb and retain adsorbate molecules selectively, and this selectivity can be reduced by competition for these active groups by the displacing solvent. Release is also governed by the surface coverage of the particles and increases as coverage approaches the monolayer. PMID:3383818

  6. First principles studies for formation mechanism and properties of ethylene molecule adsorbing on diamond (100) surface.

    PubMed

    Jin, Hao; Dai, Ying; Long, Run; Guo, Meng; Huang, Baibiao; Zhang, Ruiqin

    2008-03-21

    We employed density functional theory within the generalized gradient approximation to investigate the diamond (100) surface, with hydrogen and ethylene terminations. The radical chain reaction is investigated by slab models, and two possible adsorption ways are found according to our calculations. In addition, the electron affinity of H-terminated diamond is also calculated, which indicates that the existence of negative electron affinity of H-C (100) surface provides a necessary condition for initiating radical chain reaction. Our results also imply that ethylene molecules can form strong C-C covalent bonds with diamond surface, which make it more resistant against degradation processes. Furthermore, according to the analysis of electronic structures, we have found localized gap state above the valence band, which is mainly contributed by the interaction between diamond surface and ethylene molecule and can weaken the surface conductivity of the adsorbed diamond.

  7. Molecular resonant dissociation of surface-adsorbed molecules by plasmonic nanoscissors

    NASA Astrophysics Data System (ADS)

    Zhang, Zhenglong; Sheng, Shaoxiang; Zheng, Hairong; Xu, Hongxing; Sun, Mengtao

    2014-04-01

    The ability to break individual bonds or specific modes in chemical reactions is an ardently sought goal by chemists and physicists. While photochemistry based methodologies are very successful in controlling e.g. photocatalysis, photosynthesis and the degradation of plastic, it is hard to break individual molecular bonds for those molecules adsorbed on the surface because of the weak light-absorption in molecules and the redistribution of the resulting vibrational energy both inside the molecule and to its surrounding environment. Here we show how to overcome these obstacles with a plasmonic hot-electron mediated process and demonstrate a new method that allows the sensitive control of resonant dissociation of surface-adsorbed molecules by `plasmonic' scissors. To that end, we used a high-vacuum tip-enhanced Raman spectroscopy (HV-TERS) setup to dissociate resonantly excited NC2H6 fragments from Malachite green. The surface plasmons (SPs) excited at the sharp metal tip not only enhance the local electric field to harvest the light incident from the laser, but crucially supply `hot electrons' whose energy can be transferred to individual bonds. These processes are resonant Raman, which result in some active chemical bonds and then weaken these bonds, followed by dumping in lots of indiscriminant energy and breaking the weakest bond. The method allows for sensitive control of both the rate and probability of dissociation through their dependence on the density of hot electrons, which can be manipulated by tuning the laser intensity or tunneling current/bias voltage in the HV-TERS setup, respectively. The concepts of plasmonic scissors open up new versatile avenues for the deep understanding of in situ surface-catalyzed chemistry.The ability to break individual bonds or specific modes in chemical reactions is an ardently sought goal by chemists and physicists. While photochemistry based methodologies are very successful in controlling e.g. photocatalysis

  8. Adsorption of sodium and cesium on aggregates of C60

    NASA Astrophysics Data System (ADS)

    Harnisch, Martina; Daxner, Matthias; Scheier, Paul; Echt, Olof

    2016-09-01

    We explore the formation of C60 sodium and C60 cesium complexes in superfluid helium nanodroplets. Anomalies in mass spectra of these doped droplets reveal anomalies in the stability of ions. (C60) m Cs+ n ions ( m ≤ 6) are particularly abundant if they contain n = 6 m + 1 cesium atoms; (C60) m Cs2+ n dications ( m ≤ 3 or 5) are abundant if n = 6 m + 2. These findings are consistent with the notion that alkali metal atoms (A) transfer their valence electrons into the three-fold degenerate lowest unoccupied orbital of C60, resulting in particularly stable C60A6 building blocks. However, (C60) 4CsCs2+ n dications display an entirely different pattern; instead of an expected anomaly at n = 6 × 4 + 2 = 26 we observe a strong odd-even alternation starting at n = 6. Also surprising is the effect of adding one H2O or CO2 molecule to (C60) m Cs n mono- or dications; anomalies shift by two units as if the impurity were acting as an acceptor for two valence electrons from the alkali metal atoms.

  9. Magnetization switching in ferromagnets by adsorbed chiral molecules without current or external magnetic field.

    PubMed

    Ben Dor, Oren; Yochelis, Shira; Radko, Anna; Vankayala, Kiran; Capua, Eyal; Capua, Amir; Yang, See-Hun; Baczewski, Lech Tomasz; Parkin, Stuart Stephen Papworth; Naaman, Ron; Paltiel, Yossi

    2017-02-23

    Ferromagnets are commonly magnetized by either external magnetic fields or spin polarized currents. The manipulation of magnetization by spin-current occurs through the spin-transfer-torque effect, which is applied, for example, in modern magnetoresistive random access memory. However, the current density required for the spin-transfer torque is of the order of 1 × 10(6) A·cm(-2), or about 1 × 10(25) electrons s(-1) cm(-2). This relatively high current density significantly affects the devices' structure and performance. Here we demonstrate magnetization switching of ferromagnetic thin layers that is induced solely by adsorption of chiral molecules. In this case, about 10(13) electrons per cm(2) are sufficient to induce magnetization reversal. The direction of the magnetization depends on the handedness of the adsorbed chiral molecules. Local magnetization switching is achieved by adsorbing a chiral self-assembled molecular monolayer on a gold-coated ferromagnetic layer with perpendicular magnetic anisotropy. These results present a simple low-power magnetization mechanism when operating at ambient conditions.

  10. Magnetization switching in ferromagnets by adsorbed chiral molecules without current or external magnetic field

    PubMed Central

    Ben Dor, Oren; Yochelis, Shira; Radko, Anna; Vankayala, Kiran; Capua, Eyal; Capua, Amir; Yang, See-Hun; Baczewski, Lech Tomasz; Parkin, Stuart Stephen Papworth; Naaman, Ron; Paltiel, Yossi

    2017-01-01

    Ferromagnets are commonly magnetized by either external magnetic fields or spin polarized currents. The manipulation of magnetization by spin-current occurs through the spin-transfer-torque effect, which is applied, for example, in modern magnetoresistive random access memory. However, the current density required for the spin-transfer torque is of the order of 1 × 106 A·cm−2, or about 1 × 1025 electrons s−1 cm−2. This relatively high current density significantly affects the devices' structure and performance. Here we demonstrate magnetization switching of ferromagnetic thin layers that is induced solely by adsorption of chiral molecules. In this case, about 1013 electrons per cm2 are sufficient to induce magnetization reversal. The direction of the magnetization depends on the handedness of the adsorbed chiral molecules. Local magnetization switching is achieved by adsorbing a chiral self-assembled molecular monolayer on a gold-coated ferromagnetic layer with perpendicular magnetic anisotropy. These results present a simple low-power magnetization mechanism when operating at ambient conditions. PMID:28230054

  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. Induced IR overtone and fundamental bands of isotopic H 2 molecules adsorbed in NaCaA zeolites

    NASA Astrophysics Data System (ADS)

    Förster, H.; Frede, W.

    1984-05-01

    NIR spectroscopy has been successfully applied to surface chemical problems, using the FT transmission technique. Vibrational spectra of H 2 and D 2, adsorbed in NaA and NaCaA zeolites, have been recorded in the fundamental regions of both adsorbates and, for the first time, in the overtone region of D 2. Useful information on the properties of the adsorbed molecules can be derived from the overtone spectra of D 2 and the fine structure of the H 2 fundamental. It turns out that the properties of the D 2 molecules, e.g. dissociation energy and anharmonicity, are hardly affected by adsorption. The fine structure of the H 2 fundamental, however, indicates the rotation to be strongly hindered. The ortho-para splitting is decreased with respect to the free molecule value and approaches that for planarly rotating molecules. Due to this hindrance, the corresponding D 2 splitting is not resolved.

  13. Spins of adsorbed molecules investigated by the detection of Kondo resonance

    NASA Astrophysics Data System (ADS)

    Komeda, Tadahiro

    2014-12-01

    Surface magnetism has been one of the platforms to explore the magnetism in low dimensions. It is also a key component for the development of quantum information processes, which utilizes the spin degree of freedom. The Kondo resonance is a phenomenon that is caused by an interaction between an isolated spin and conduction electrons. First observed in the 1930s as an anomalous increase in the low-temperature resistance of metals embedded with magnetic atoms, the Kondo physics mainly studied the effects of bulk magnetic impurities in the resistivity. In the last 15 years it has undergone a revival by a scanning tunneling microscope (STM) which enables the measurement of the Kondo resonance at surfaces using an atomic scale point contact. The detection of the Kondo resonance can be a powerful tool to explore surface magnetism. In this article, I review recent studies of the surface spin of adsorbed molecules by the detection of the Kondo resonance. Researches on metal phthalocyanine (MPc) and porphyrin molecules will be examined. In addition, the Kondo resonance for double-decker lanthanoide Pc molecules will be discussed. Some of the double-decker Pc molecules show single-molecule magnet (SMM) behavior, which attracts attention as a material for electronic devices. For both classes, the ligand plays a crucial role in determining the parameters of the Kondo resonance, such as the Kondo temperature and the change of the shape from peak to Fano-dip. In addition, the spin in delocalized molecular orbital forms the Kondo resonance, which shows significant differences from the Kondo resonance formed by the metal spins. Since molecular orbital can be tuned in a flexible manner by the design of the molecule, the Kondo resonance formed by delocalized molecular orbital might expand the knowledge of this field.

  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. Non-IPR C60 solids.

    PubMed

    Löffler, Daniel; Bajales, Noelia; Cudaj, Marcus; Weis, Patrick; Lebedkin, Sergei; Bihlmeier, Angela; Tew, David P; Klopper, Wim; Böttcher, Artur; Kappes, Manfred M

    2009-04-28

    Films comprising predominantly novel isomers of C(60) [=C(60)(nIPR)] have been generated by low energy ion beam deposition of vibronically excited C(60)(+) onto graphite followed by selective sublimation of C(60)(I(h)) from the deposited isomer mixture. The incident ions were generated by electron impact ionization/fragmentation of sublimed C(70). Images of the C(60)(nIPR) films obtained by applying atomic force microscopy show aggregates, which we attribute to covalently interlinked C(60)(nIPR) units. The covalent bonds are inferred from the significantly higher thermal stability of the C(60)(nIPR) films compared to the C(60)(I(h)) van der Waals solid-as measured by thermal desorption with mass spectrometric detection of the C(60) mass channel (the only desorbable species). In contrast to the characteristic doublet structure of the occupied valence band in the ultraviolet photoelectron spectrum of pure C(60)(I(h)), the valence band of C(60)(nIPR) films exhibits a triplet feature with the additional peak occurring at a binding energy of approximately 2.6 eV. This is an indicator of the electronic modifications induced by intermolecular bonding. C(60)(nIPR) films exhibit a narrower band gap than found for C(60)(I(h)). They also have significantly different chemical reactivity toward incorporation of thermal energy deuterium atoms. In order to model the experimental photoelectron spectra, various covalently linked oligomers of (#1809)C(60)(C(2v)), the second most stable conventional 60-atom fullerene cage, were calculated by means of the density functional theory. These spectral predictions together with analogous previous observations on related fullerene solids such as C(58) lead us to infer that C(60)(nIPR) films consist of fullerene cage isomers containing one or more adjacent pentagon pairs, which mediate covalent cage-cage interconnection.

  16. Magnetic transitions induced by tunneling electrons in individual adsorbed M -phthalocyanine molecules ( M=Fe and Co)

    NASA Astrophysics Data System (ADS)

    Gauyacq, Jean-Pierre; Novaes, Frederico D.; Lorente, Nicolás

    2010-04-01

    We report on a theoretical study of magnetic transitions induced by tunneling electrons in individual adsorbed M -Phthalocyanine (M-Pc) molecules where M is a metal atom: Fe-Pc on a Cu(110)(2×1)-O surface and Co-Pc layers on Pb(111) islands. The magnetic transitions correspond to the change in orientation of the spin angular momentum of the metal ion with respect to the surroundings and possibly an applied magnetic field. The adsorbed Fe-Pc system is studied with a density-functional-theory-transport approach showing that (i) the magnetic structure of the Fe atom in the adsorbed Fe-Pc is quite different from that of the free Fe atom or of other adsorbed Fe systems and (ii) that injection of electrons (holes) into the Fe atom in the adsorbed Fe-Pc molecule dominantly involves the Fe3dz2 orbital. These results fully specify the magnetic structure of the system and the process responsible for magnetic transitions. The dynamics of the magnetic transitions induced by tunneling electrons is treated in a strong-coupling approach. The Fe-Pc treatment is extended to the Co-Pc case. The present calculations accurately reproduce the strength of the magnetic transitions as observed by magnetic inelastic electron tunneling spectroscopy experiments; in particular, the dominance of the inelastic current in the conduction of the adsorbed M-Pc molecule is accounted for.

  17. Room temperature differential conductance measurements of triethylamine molecules adsorbed on Si(001).

    PubMed

    Naitabdi, Ahmed; Rochet, François; Carniato, Stéphane; Bournel, Fabrice; Gallet, Jean-Jacques

    2016-08-17

    We have measured the differential conductance of the triethylamine molecule (N(CH2CH3)3) adsorbed on Si(001)-2 × 1 at room temperature using scanning tunneling spectroscopy. Triethylamine can be engaged in a dative bonding with a silicon dimer, forming a Si-Si-N(CH2CH3)3 unit. We have examined the datively bonded adduct, either as an isolated molecule, or within an ordered molecular domain (reconstructed 4 × 2). The differential conductance curves, supported by DFT calculations, show that in the explored energy window (±2.5 near the Fermi level) the main features stem from the uncapped dangling bonds of the reacted dimer and of the adjacent unreacted ones that are electronically coupled The formation of a molecular domain, in which one dimer in two is left unreacted, is reflected in a shift of the up dimer atom occupied level away from the Fermi level, likely due to an increased π-bonding strength. In stark contrast with the preceding, pairs of dissociated molecule (a minority species) are electronically decoupled from the dimer dangling bond states. DFT calculation show that the lone-pair of the Si-N(CH2CH3)2 is a shallow level, that is clearly seen in the differential conductance curve.

  18. Surface self-diffusion of organic molecules adsorbed in porous silicon.

    PubMed

    Valiullin, Rustem; Kortunov, Pavel; Kärger, Jörg; Timoshenko, Viktor

    2005-03-31

    The pulsed field gradient nuclear magnetic resonance method has been employed to probe self-diffusion of organic guest molecules adsorbed in porous silicon with a 3.6 nm pore size. The molecular self-diffusion coefficient and intrapore adsorption were simultaneously measured as a function of the external vapor pressure. The latter was varied in a broad range to provide pore loading from less than monolayer surface coverage to full pore saturation. The measured diffusivities are found to be well-correlated with the adsorption isotherms. At low molecular concentrations in the pores, corresponding to surface coverages of less than one monolayer, the self-diffusion coefficient strongly increases with increasing concentration. This observation is attributed to the occurrence of activated diffusion on a heterogeneous surface. Additional experiments in a broad temperature range and using binary mixtures confirm this hypothesis.

  19. Density functional analysis of gaseous molecules adsorbed on metal ion/defective nano-sheet graphene

    NASA Astrophysics Data System (ADS)

    Deng, Jin-Pei; Chuang, Wen-Hua; Tai, Chin-Kuen; Kao, Hsien-Chang; Pan, Jiunn-Hung; Wang, Bo-Cheng

    2016-11-01

    Density functional theory was applied to calculate the adsorption property of metal/hexa-vacancy defective graphene (denoted as HDG-M, M: Fe2+, Co2+, Ni2+, Cu2+ and Zn2+) with O- and N-dopants. We investigate the adsorption properties of these complexes between gaseous molecules and HDG-M. Our results show that HDG-Cu has a high selectivity for O2, but HDG-Fe has a good ability to capture many gases such as CO, NO and O2. Our calculations could provide useful information for designing new graphene-based adsorbents to remove undesired gases, which may poison the metal catalysts in reaction processes.

  20. Adsorbed Oxygen Molecules as a Source of Flux Noise in SQUIDs

    NASA Astrophysics Data System (ADS)

    Wang, Hui; Wang, Zhe; Hu, Jun; Shi, Chuntai; Yu, Clare C.; Wu, Ruqian; Department of Physics, Fudan University, Shanghai 200433, China Collaboration; Department of Physics; Astronomy, University of California, Irvine, CA 92697-4575, USA Collaboration

    2015-03-01

    A major obstacle for using superconducting quantum interference devices (SQUIDs) as qubits is the flux noise generated by fluctuating magnetic spins on the surface of SQUIDs. Using density functional theory (DFT) calculations, we investigated O2 adsorbates and various vacancies on an α-alumina surface as spin candidates. Their spectroscopic features are directly compared to experimental data using the x-ray magnetic circular dichroism. The calculated magnetic anisotropy energy for the spin of O2 to rotate within a plane perpendicular to the axis of the O-O bond is only about 12 mK (or ~ 1 μeV) so we believe that O2 molecules are the main source of flux noise in Al SQUIDs. Work at Fudan was supported by the 1000-Telent funds. Work at UCI was supported by DOE-BES (Grant No. DE- FG02-05ER46237) and by NERSC for computing time.

  1. The surface plasmon enhancement effect on adsorbed molecules at elevated temperatures

    NASA Astrophysics Data System (ADS)

    Chiang, H.-P.; Leung, P. T.; Tse, W. S.

    1998-02-01

    The surface plasmon enhancement effect on adsorbed molecules at elevated substrate temperatures is studied theoretically using surface enhanced Raman scattering (SERS) as an example. The surface structure is idealized to be a monodisperse spherical particle with its nonlocal dielectric response accounted for. The temperature effects are modeled using a temperature-dependent collision frequency in the Drude model. Numerical results show that only a small decrease in the SERS enhancement ratio occurs for temperatures up to the melting point of the substrate, even for scattering close to the surface plasmon resonance frequency of the metal. More definitive results are subjected to more realistic modeling as well as systematic experimental studies. The implication of this result to other surface photochemical processes is discussed.

  2. Infrared spectroscopy of fullerene C60/anthracene adducts

    NASA Astrophysics Data System (ADS)

    García-Hernández, D. A.; Cataldo, F.; Manchado, A.

    2013-09-01

    Recent Spitzer Space Telescope observations of several astrophysical environments such as planetary nebulae, reflection nebulae and R Coronae Borealis stars show the simultaneous presence of mid-infrared features attributed to neutral fullerene molecules (i.e. C60) and polycyclic aromatic hydrocarbons (PAHs). If C60 fullerenes and PAHs coexist in fullerene-rich space environments, then C60 may easily form adducts with a number of different PAH molecules, at least with catacondensed PAHs. Here we present the laboratory infrared spectra (˜2-25 μm) of C60 fullerene and anthracene Diels-Alder mono- and bis-adducts as produced by sonochemical synthesis. We find that C60/anthracene Diels-Alder adducts display spectral features strikingly similar to those from C60 (and C70) fullerenes and other unidentified infrared emission features. Thus, fullerene adducts - if formed under astrophysical conditions and are stable/abundant enough - may contribute to the infrared emission features observed in fullerene-containing circumstellar/interstellar environments.

  3. Striped domains at the pentacene:C60 interface

    NASA Astrophysics Data System (ADS)

    Dougherty, Daniel B.; Jin, Wei; Cullen, William G.; Reutt-Robey, Janice E.; Robey, Steven W.

    2009-01-01

    Scanning tunneling microscopy observations of the initial growth stages of the first layer of pentacene on a monolayer film of C60 on Ag(111) are presented. Pentacene films nucleate and grow with molecules standing up at the pentacene:C60 interface similar to thin film phases observed on weakly interacting substrates such as SiO2. Unlike reported thin film pentacene phases, those on 1 monolayer C60/Ag(111) exhibit a striated morphology with domains of 4 nm nominal width. This long range pattern of periodic pentacene displacements relative to the substrate is the response to stress induced in the pentacene film by its interaction with the rigid C60 support.

  4. 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.

  5. Electronic structures and nonlinear optical properties of highly deformed halofullerenes C(3v) C60F18 and D(3d) C60Cl30.

    PubMed

    Tang, Shu-Wei; Feng, Jing-Dong; Qiu, Yong-Qing; Sun, Hao; Wang, Feng-Di; Chang, Ying-Fei; Wang, Rong-Shun

    2010-11-15

    Electronic structures and nonlinear optical properties of two highly deformed halofullerenes C(3v) C(60)F(18) and D(3d) C(60)Cl(30) have been systematically studied by means of density functional theory. The large energy gaps (3.62 and 2.61 eV) between the highest occupied and lowest unoccupied molecular orbitals (HOMOs and LUMOs) and the strong aromatic character (with nucleus-independent chemical shifts varying from -15.08 to -23.71 ppm) of C(60)F(18) and C(60)Cl(30) indicate their high stabilities. Further investigations of electronic property show that C(60)F(18) and C(60)Cl(30) could be excellent electron acceptors for potential photonic/photovoltaic applications in consequence of their large vertical electron affinities. The density of states and frontier molecular orbitals are also calculated, which present that HOMOs and LUMOs are mainly distributed in the tortoise shell subunit of C(60)F(18) and the aromatic [18] trannulene ring of C(60)Cl(30), and the influence from halogen atoms is secondary. In addition, the static linear polarizability and second-order hyperpolarizability of C(60)F(18) and C(60)Cl(30) are calculated using finite-field approach. The values of and for C(60)F(18) and C(60)Cl(30) molecules are significantly larger than those of C(60) because of their lower symmetric structures and high delocalization of pi electrons.

  6. Reducing HAuCl4 by the C60 dianion: C60-directed self-assembly of gold nanoparticles into novel fullerene bound gold nanoassemblies

    NASA Astrophysics Data System (ADS)

    Liu, Wei; Gao, Xiang

    2008-10-01

    The C60 dianion is used to reduce tetrachloroauric acid (HAuCl4) for the first time; three-dimensional C60 bound gold (Au-C60) nanoclusters are obtained from C60-directed self-assembly of gold nanoparticles due to the strong affinities of Au-C60 and C60-C60. The process was monitored in situ by UV-vis-NIR spectroscopy. The resulting Au-C60 nanoclusters were characterized using transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy-dispersive spectroscopy (EDS), x-ray powder diffraction (XRD), x-ray photoelectron spectroscopy (XPS), and FT-IR and Raman spectroscopies. TEM demonstrates the formation of 3D nanonetwork aggregates, which are composed of discrete gold nanocores covered with a C60 monolayer. The SAED and XRD patterns indicate that the gold nanocores inside the capped C60 molecules belong to the face-centred cubic crystal structure, while the C60 molecules are amorphous. The EDS and XPS measurements validate that the Au-C60 nanoclusters contain only Au and C elements and Au3+ is reduced to Au0. FT-IR spectroscopy shows the chemiadsorption of C60 to the gold nanocores, while Raman spectroscopy demonstrates the electron transfer from the gold nanocores to the chemiadsorbed C60 molecules. Au-C60 nanoclusters embedded in tetraoctyl-n-ammonium bromide (TOAB) on glassy carbon electrodes (GCEs) have been fabricated and have shown stable and well-defined electrochemical responses in aqueous solution.

  7. Adsorption and self-assembly of fullerenes on Si(111)√{ 3 } ×√{ 3 }-Ag: C60 versus C70

    NASA Astrophysics Data System (ADS)

    Olyanich, D. A.; Mararov, V. V.; Utas, T. V.; Zotov, A. V.; Saranin, A. A.

    2016-11-01

    Behavior of C60 and C70 fullerenes adsorbed onto Si(111)√{ 3 } ×√{ 3 }-Ag is compared on the basis of STM observations. Such characteristics as sticking coefficient, migration rate, attachment/detachment rate from the molecular islands are considered. Room-temperature sticking coefficient for C70 is slightly greater than that for C60. Due to their non-spherical shape, C70 are less mobile than spherical C60. For both types of fullerenes, mobility of molecules on the fullerene layer is significantly retarded as compared to that on bare Si(111)√{ 3 } ×√{ 3 }-Ag surface. Self-assembly of C60 obeys layer-by-layer growth mode, while C70 follows multi-layer mode, a sign of a greater Ehrlich-Schwoebel barrier. Alternating deposition of C60 and C70 paves the way to fabricate planar C60/C70 heterostructures with the most promising results being obtained with nanostructured islands grown on C60 monomolecular layer.

  8. C60-PMO: periodic mesoporous buckyballsilica.

    PubMed

    Whitnall, Wesley; Cademartiri, Ludovico; Ozin, Geoffrey A

    2007-12-19

    Here we report the first documented synthesis of a periodic mesoporous organosilica (PMO), that contains a multiply bonded C60 moiety integrated into the silica channel walls of the material, dubbed C60-PMO. This is accomplished through the acid-catalyzed co-assembly, of C60(NHCH2CH2CH2Si(OEt)3)x and tetraethylorthosilicate (TEOS) with a polyethyleneoxide-polylpropyleneoxide-polyethyleneoxide triblock copolymer template. The percentage of C60 in the final material was estimated to be a minimum of 63 vol %, but potentially as high as 91 vol %. The effects of the synthesis conditions on the mesostructure of the resulting materials are examined. In particular, we demonstrate that the C60 is uniformly distributed throughout the entire sample by the use of energy dispersive X-ray fluorescence (EDX) analysis and an OsO4 label bonded to the C60.

  9. [Antiamyloid properties of fullerene C60 derivatives].

    PubMed

    Bobylev, A G; Shpagina, M D; Bobyleva, L G; Okuneva, A D; Piotrovskiĭ, L B; Podlubnaia, Z A

    2012-01-01

    A comparative estimation of the ability of complexes of fullerene C60 with polyvinylpyrrolidone and fullerene C60 derivatives (the sodium salt of the polycarboxylic derivative of fullerene C60, sodium fullerenolate), has been carried out. The fullerenes destroyed amyloid fibrils of the Abeta(1-42) peptide of the brain and the muscle X-protein. A study of the effect of fullerenes on muscle actin showed that complexes of fullerene C60 with polyvinylpyrrolidone and sodium fullerenolate did not prevent the filament formation of actin, nor did they destroy its filaments in vitro. Conversely, sodium salt of the polycarboxylic derivative of fullerene C60 destroyed actin filaments and prevented their formation. It was concluded that sodium fullerenolate and complexes of fullerene C60 with polyvinylpyrrolidone are the most effective antiamyloid compounds among the fullerenes examined.

  10. Photoelectron spectroscopy of C60Fn- and C60Fm2- (n = 17, 33, 35, 43, 45, 47; m = 34, 46) in the gas phase and the generation and characterization of C1-C60F47- and D2-C60F44 in solution.

    PubMed

    Wang, Xue-Bin; Chi, Chaoxian; Zhou, Mingfei; Kuvychko, Igor V; Seppelt, Konrad; Popov, Alexey A; Strauss, Steven H; Boltalina, Olga V; Wang, Lai-Sheng

    2010-02-04

    A photoelectron spectroscopy investigation of the fluorofullerene anions C(60)F(n)(-) (n = 17, 33, 35, 43, 45, 47) and the doubly charged anions C(60)F(34)(2-) and C(60)F(46)(2-) is reported. The first electron affinities for the corresponding neutral molecules, C(60)F(n), were directly measured and were found to increase as n increased, reaching the extremely high value of 5.66 +/- 0.10 eV for C(60)F(47). Density functional calculations suggest that the experimentally observed species C(60)F(17)(-), C(60)F(35)(-), and C(60)F(47)(-) were each formed by reductive defluorination of the parent fluorofullerene, C(3v)-C(60)F(18), C(60)F(36) (a mixture of isomers), and D(3)-C(60)F(48), respectively, without rearrangement of the remaining fluorine atoms. The DFT-predicted stability of C(60)F(47)(-) was verified by its generation by chemical reduction from D(3)-C(60)F(48) in chloroform solution at 25 degrees C and its characterization by mass spectrometry and (19)F NMR spectroscopy. Further reductive defluorination of C(60)F(47)(-) in solution resulted in the selective generation of a new fluorofullerene, D(2)-C(60)F(44), which was also characterized by mass spectrometry and (19)F NMR spectroscopy.

  11. Structural transformation of biochar black carbon by C60 superstructure: Environmental implications

    USDA-ARS?s Scientific Manuscript database

    Aqueous fullerene C60 nanoparticles (nC60) are frequently considered within the environmental engineering community as the aggregate of 60-carbon molecules. This study employed transmission electron microscopy (TEM) and x-ray diffraction (XRD) to demonstrate that nC60 formed via prolonged stirring ...

  12. Effect of Adsorbed Alcohol Layers on the Behavior of Water Molecules Confined in a Graphene Nanoslit: A Molecular Dynamics Study.

    PubMed

    Gao, Qingwei; Zhu, Yudan; Ruan, Yang; Zhang, Yumeng; Zhu, Wei; Lu, Xiaohua; Lu, Linghong

    2017-09-11

    With the rapid development of a two-dimensional (2D) nanomaterial, the confined liquid binary mixture has attracted increasing attention, which has significant potential in membrane separation. Alcohol/water is one of the most common systems in liquid-liquid separation. As one of the most focused systems, recent studies have found that ethanol molecules were preferentially adsorbed on the inner surface of the pore wall and formed an adsorbed ethanol layer under 2D nanoconfinement. To evaluate the effect of the alcohol adsorption layer on the mobility of water molecules, molecular simulations were performed to investigate four types of alcohol/water binary mixtures confined under a 20 Å graphene slit. Residence times of the water molecules covering the alcohol layer were in the order of methanol/water < ethanol/water < 1-propanol/water < 1-butanol/water. Detailed microstructural analysis of the hydrogen bonding (H-bond) network elucidated the underlying mechanism on the molecular scale in which a small average number of H-bonds between the preferentially adsorbed alcohol molecules and the surrounding water molecules could induce a small degree of damage to the H-bond network of the water molecules covering the alcohol layer, resulting in the long residence time of the water molecules.

  13. 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.

  14. Electronic structure and binding geometry of tetraphenylporphyrin-derived molecules adsorbed on metal and metal oxide surfaces

    NASA Astrophysics Data System (ADS)

    Coh, Senia

    Tetraphenylporphyrin (TPP)-derived molecules have been studied extensively as efficient photosensitizers when chemisorbed on the metal oxide substrates in dye-sensitized solar cells. Still, many fundamental electronic properties of the dye/oxide interface are not understood and need careful consideration. In this thesis we present a comprehensive study of the electronic structure, energy level alignment and the adsorption geometry of the TPP-derived dye molecules adsorbed on TiO2(110), ZnO(1120) and Ag(100) single crystal surfaces using ultra-high vacuum (UHV) based surface sensitive techniques. The alignment of the molecular energy levels with respect to the TiO 2 and ZnO band edges for all TPP-derived molecules we studied was found to be insensitive to either the nature of the functional groups located on the phenyl rings, presence of zinc as a central metal ion and different binding geometry of the molecules. Binding geometry, molecule-molecule interaction and the aggregation effects in the adsorbed layer, that were observed in the UV-visible spectra of the molecules adsorbed on ZnO substrate were not observed in the ultraviolet photoemission (UPS) and inverse photoemission (IPS) spectra of the occupied and unoccupied molecular states. Using near edge X-ray absorption fine structure (NEXAFS) and scanning tunneling microscopy (STM), binding geometry of the two representative TPP-derivatives was directly determined to be upright, with the porphyrin ring under large angle with respect to the surface for the p-ZnTCPP molecules and with the porphyrin ring parallel to the surface for the m-ZnTCPP molecules. We observe that the energies and the energy level alignment of the ZnTPP molecular levels measured in UPS and IPS depend on the substrate on which the molecules are adsorbed (Ag(100) or TiO2(110) single crystal surfaces). The differences are attributed to different charge screening properties of these two materials. Image charges created in the substrates during

  15. Ro-vibrational Stark effect on H2 and D2 molecules adsorbed in NaA zeolite

    NASA Astrophysics Data System (ADS)

    Bras, N.

    1999-03-01

    In order to explain the induced infrared bands of H2 and D2 adsorbed in NaA zeolites the Stark effect on the ro-vibrational levels of these molecules is considered for electric fields created by various charge distributions. The shift and intensity of the induced ro-vibration transitions are calculated.

  16. 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 applicants...

  17. 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...

  18. 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

  19. Entrapping of exohedral metallofullerenes in carbon nanotubes: (CsC60)n@SWNT nano-peapods.

    PubMed

    Sun, Bao-Yun; Sato, Yuta; Suenaga, Kazutomo; Okazaki, Toshiya; Kishi, Naoki; Sugai, Toshiki; Bandow, Shunji; Iijima, Sumio; Shinohara, Hisanori

    2005-12-28

    Exohedral C60-based metallofullerenes, CsC60, have been synthesized and successfully encapsulated into single-wall carbon nanotubes (SWNTs) in high yield by reducing C60 molecules into anions. High-resolution transmission electron microscopy (HRTEM) images and in situ electron energy loss spectroscopy (EELS) indicate that Cs atoms and C60 molecules align within SWNTs as CsC60 exohedral metallofullerenes, and that the formal charge state of encaged CsC60 is expressed as Cs+1C60-1. The present peapods with the exohedral metallofullerenes provide a new insight and the possibility to fine-tune the electronic and transport properties of carbon nanotubes.

  20. Micro-differential thermal analysis detection of adsorbed explosive molecules using microfabricated bridges.

    PubMed

    Senesac, Larry R; Yi, Dechang; Greve, Anders; Hales, Jan H; Davis, Zachary J; Nicholson, Don M; Boisen, Anja; Thundat, Thomas

    2009-03-01

    Although micromechanical sensors enable chemical vapor sensing with unprecedented sensitivity using variations in mass and stress, obtaining chemical selectivity using the micromechanical response still remains as a crucial challenge. Chemoselectivity in vapor detection using immobilized selective layers that rely on weak chemical interactions provides only partial selectivity. Here we show that the very low thermal mass of micromechanical sensors can be used to produce unique responses that can be used for achieving chemical selectivity without losing sensitivity or reversibility. We demonstrate that this method is capable of differentiating explosive vapors from nonexplosives and is additionally capable of differentiating individual explosive vapors such as trinitrotoluene, pentaerythritol tetranitrate, and cyclotrimethylenetrinitromine. This method, based on a microfabricated bridge with a programmable heating rate, produces unique and reproducible thermal response patterns within 50 ms that are characteristic to classes of adsorbed explosive molecules. We demonstrate that this micro-differential thermal analysis technique can selectively detect explosives, providing a method for fast direct detection with a limit of detection of 600x10(-12) g.

  1. Micro differential thermal analysis detection of adsorbed explosive molecules using microfabricated bridges

    SciTech Connect

    Senesac, Larry R; Yi, Dechang; Greve, Anders; Hales, Jan; Davis, Zachary; Nicholson, Don M; Boisen, Anja; Thundat, Thomas George

    2009-01-01

    Although micromechanical sensors enable chemical vapor sensing with unprecedented sensitivity using variations in mass and stress, obtaining chemical selectivity using the micromechanical response still remains as a crucial challenge. Chemoselectivity in vapor detection using immobilized selective layers that rely on weak chemical interactions provides only partial selectivity. Here we show that the very low thermal mass of micromechanical sensors can be used to produce unique responses that can be used for achieving chemical selectivity without losing sensitivity or reversibility. We demonstrate that this method is capable of differentiating explosive vapors from nonexplosives and is additionally capable of differentiating individual explosive vapors such as trinitrotoluene, pentaerythritol tetranitrate, and cyclotrimethylenetrinitromine. This method, based on a microfabricated bridge with a programmable heating rate, produces unique and reproducible thermal response patterns within 50 ms that are characteristic to classes of adsorbed explosive molecules. We demonstrate that this micro-differential thermal analysis technique can selectively detect explosives, providing a method for fast direct detection with a limit of detection of 600 x 10{sup -12} g.

  2. Polarization effects in C60 fullerene complexes of alkali ions

    NASA Astrophysics Data System (ADS)

    Ruiz, A.; Hernández-Rojas, J.; Bretón, J.; Gomez Llorente, J. M.

    1998-09-01

    We introduce a secular semiempirical model of the Pariser-Parr-Pople type to reproduce the electronic structure and polarizability of the C60 fullerene. The model is then used to simulate the response of this molecule to an electric charge and estimate its polarization energy. By expressing the charge potential at the C60-cage surface as a multipole expansion, an analytical form is obtained for the polarization energy. Application of these results to endo- and exohedral complexes of alkali ions gives data in rather good agreement with recent ab initio calculations [Hira and Ray, Phys. Rev. A 52, 141 (1995)].

  3. 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.

  4. 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.

  5. Classical and quantum studies of the photodissociation of a HX (X=Cl,F) molecule adsorbed on ice.

    PubMed

    Woittequand, S; Duflot, D; Monnerville, M; Pouilly, B; Toubin, C; Briquez, S; Meyer, H-D

    2007-10-28

    The photodissociation dynamics of a HX (X = Cl,F) molecule adsorbed on a hexagonal ice surface at T = 0 K is studied using time-dependent quantum wave packets and quasiclassical trajectories. The relevant potential energy surfaces are calculated using high-level ab initio methods. We present here two dimensional calculations for the dynamics of the hydrogen photofragment for both HCl and HF molecules. The purpose of this paper is to compare the photodissociation dynamics of the two molecules which are adsorbed on the ice surface with different equilibrium geometries. The total photodissociation cross section and the angular distribution are calculated. The comparison with classical trajectory calculations provides evidence for typical quantum effects and reveals rainbow structures.

  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.

  7. Electric field effect observed on the infrared spectra of the N2O molecule adsorbed in NaA zeolite

    NASA Astrophysics Data System (ADS)

    Bras, N.; Cohen de Lara, E.

    1995-05-01

    The spectrum of the N2O molecule adsorbed in the cavity of NaA zeolite presents two main components for each of the stretching vibrational modes. It is assumed that they correspond to molecules parallel and antiparallel to the electric field of the inner surface of the zeolite cavity. In order to verify this assumption, the frequency shifts and the intensities of these components have been calculated for the two orientations of the molecule with respect to the field, by applying the model of Bishop for the vibrational Stark effect. These calculations require the knowledge of molecular quantities such as derivatives of permanent electric moments and polarizability.

  8. Direct comparison of the electronic coupling efficiency of sulfur and selenium anchoring groups for molecules adsorbed onto gold electrodes

    NASA Astrophysics Data System (ADS)

    Patrone, L.; Palacin, S.; Bourgoin, J. P.; Lagoute, J.; Zambelli, T.; Gauthier, S.

    2002-08-01

    We performed air and ultra-high vacuum scanning tunneling microscopy experiments in order to compare the electronic coupling provided by S and by Se used as alligator clips for bisthiol- and biselenol-terthiophene molecules adsorbed onto gold. The molecules were inserted in a dodecanethiol self-assembled monolayer. Their apparent height above the dodecanethiol matrix was used as a measure of the electronic coupling strength corresponding to S and Se, respectively. We show that the insertion behaviors of the two molecules are qualitatively the same, and that Se provides systematically a better coupling link than S whatever the tunneling conditions.

  9. Direct comparison of the electronic coupling efficiency of sulfur and selenium alligator clips for molecules adsorbed onto gold electrodes

    NASA Astrophysics Data System (ADS)

    Patrone, L.; Palacin, S.; Bourgoin, J. P.

    2003-05-01

    Scanning tunneling microscopy experiments have been performed to compare the electronic coupling provided by S and by Se used as alligator clips for bisthiol- and biselenol-terthiophene molecules adsorbed onto gold. The molecules were inserted in a dodecanethiol (DT) self-assembled monolayer. Their apparent height above the dodecanethiol matrix was used as a measure of the electronic coupling strength corresponding to S and Se, respectively. We show that the insertion behaviors of the two molecules are qualitatively the same, and that Se provides systematically a better coupling link than S, whatever the tunneling conditions.

  10. Non-Engineered Nanoparticles of C60

    PubMed Central

    Deguchi, Shigeru; Mukai, Sada-atsu; Sakaguchi, Hide; Nonomura, Yoshimune

    2013-01-01

    We discovered that rubbing bulk solids of C60 between fingertips generates nanoparticles including the ones smaller than 20 nm. Considering the difficulties usually associated with nanoparticle production by pulverisation, formation of nanoparticles by such a mundane method is unprecedented and noteworthy. We also found that nanoparticles of C60 could be generated from bulk solids incidentally without deliberate engineering of any sort. Our findings imply that there exist highly unusual human exposure routes to nanoparticles of C60, and elucidating formation mechanisms of nanoparticles is crucial in assessing their environmental impacts. PMID:23807024

  11. Optimal covering of C60 fullerene by rare gases

    NASA Astrophysics Data System (ADS)

    Acosta-Gutiérrez, S.; Bretón, J.; Llorente, J. M. Gomez; Hernández-Rojas, J.

    2012-08-01

    Putative global energy minima of clusters formed by the adsorption of rare gases on a C60 fullerene molecule, C60XN (X=Ne, Ar, Kr, Xe; N ⩽ 70), are found using basin-hopping global optimization in an empirical potential energy surface. The association energies per rare gas atom as a function of N present two noticeable minima for Ne and Ar and just one for Kr and Xe. The minimum with the smallest N is the deepest one and corresponds to an optimal packing monolayer structure; the other one gives a monolayer with maximum packing. For Kr and Xe, optimal and maximum packing structures coincide. By using an isotropic average form of the X-C60 interaction, we have established the relevance of the C60 surface corrugation on the cluster structures. Quantum effects are relevant for Ne clusters. The adsorption of these rare gases on C60 follows patterns that differ significantly from the ones found recently for He by means of experimental and theoretical methods.

  12. Photocycloaddition of anthracene to excited C-60

    SciTech Connect

    Gol`dshleger, N.F.; Denisov, N.N.; Lobach, A.S.

    1995-02-01

    The ability to participate in photochemical cycloaddition reactions is characteristic feature of chromophores with a carbon double bond. In this work, the authors demonstrate the formation of an adduct by cycloaddition of anthracene to the triplet-excited C-60 fullerene under anaerobic conditions, which provides a straight forward way to synthesize new derivatives of C-60 fullerenes. Reaction methods, conditions, and mechanisms are included along with the characterization of the fullerene derivative with IR, MS, and NMR methods.

  13. Characteristics of multivalent impurity doped C 60 films grown by MBE

    NASA Astrophysics Data System (ADS)

    Nishinaga, Jiro; Aihara, Tomoyuki; Kawaharazuka, Atsushi; Horikoshi, Yoshiji

    2007-04-01

    Metal-doped C 60 films (aluminum, gallium and germanium) are grown on GaAs and quartz glass substrates by solid source molecular beam epitaxy. Mechanical and optical properties of the films are investigated by Vickers hardness test and photoluminescence (PL) measurement. Vickers hardness values of all the impurity-doped C 60 films are considerably enhanced. PL peaks of the electron transition between the highest occupied molecular orbital and the lowest unoccupied molecular orbital states of C 60 molecules are confirmed in Al-doped and Ga-doped C 60 films, but not in Ge-doped C 60 films. Optimized bonding structures of these impurity atoms to C 60 molecules are determined by using ab initio calculations. Stable covalent bonds between impurities and C 60 molecules are verified to be formed. The impurity atoms may act as bridges between C 60 molecules. The distortion of C 60 cages due to the bonding with metals is confirmed. In the Al- and Ga-doped C 60 films, this distortion probably makes the dipole forbidden transition relieved. The binding energies are found to be related to the experimentally determined Vickers hardness.

  14. Selective binding of single-stranded DNA-binding proteins onto DNA molecules adsorbed on single-walled carbon nanotubes.

    PubMed

    Nii, Daisuke; Hayashida, Takuya; Yamaguchi, Yuuki; Ikawa, Shukuko; Shibata, Takehiko; Umemura, Kazuo

    2014-09-01

    Single-stranded DNA-binding (SSB) proteins were treated with hybrids of DNA and single-walled carbon nanotubes (SWNTs) to examine the biological function of the DNA molecules adsorbed on the SWNT surface. When single-stranded DNA (ssDNA) was used for the hybridization, significant binding of the SSB molecules to the ssDNA-SWNT hybrids was observed by using atomic force microscopy (AFM) and agarose gel electrophoresis. When double-stranded DNA (dsDNA) was used, the SSB molecules did not bind to the dsDNA-SWNT hybrids in most of the conditions that we evaluated. A specifically modified electrophoresis procedure was used to monitor the locations of the DNA, SSB, and SWNT molecules. Our results clearly showed that ssDNA/dsDNA molecules on the SWNT surfaces retained their single-stranded/double-stranded structures.

  15. Angular resolved photoionization of C60 by femtosecond laser pulses

    NASA Astrophysics Data System (ADS)

    Li, Hui; Wang, Zhenhua; Suessmann, Frederik; Zherebtsov, Sergey; Skruszewicz, Slawomir; Tiggesbaeumker, Josef; Fennel, Thomas; Meiwes-Broer, Karl-Heinz; Cocke, C.; Kling, Matthias; JRM laboratory, Kansas State University Team; University of Rostock Collaboration; Max-Planck InstitutQuantumoptik Collaboration

    2013-03-01

    Neutral C60 molecules are ionized by intense femtosecond laser pulses around the wavelength of 800 nm with pulse durations 4 fs and 30 fs. We measure photoelectrons utilizing velocity-map imaging (VMI) and analyze the photoelectron angular distributions. For particular photoelectron energies, these distributions might reflect the excitation and ionization of superatomic molecular orbitals (SAMOs) which have been theoretically predicted and only recently experimentally observed. SAMOs arise from the hollow core spherical structures of the C60 molecules and differ from Rydberg states of C60 by their potential to exhibit electron density within the C60 cage. We have recorded the carrier envelope phase (CEP) dependence of the electron emission for 4 fs pulses using single shot CEP-tagging. The CEP-dependent asymmetry in the electron emission is observed to strongly depend on the laser polarization. Furthermore, the amplitudes and phases of the CEP-dependent electron emission are analyzed and show that thermal electron emission can be avoided enabling a more direct comparison to theory.

  16. 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.

  17. Effects of molecule-insulator interaction on geometric property of a single phthalocyanine molecule adsorbed on an ultrathin NaCl film

    NASA Astrophysics Data System (ADS)

    Miwa, Kuniyuki; Imada, Hiroshi; Kawahara, Shota; Kim, Yousoo

    2016-04-01

    The adsorption structure and orientation of a metal-free phthalocyanine (H2Pc ) and a magnesium phthalocyanine (MgPc) on a bilayer of NaCl films were investigated both theoretically and experimentally by means of first-principles calculations based on density functional theory and by scanning tunneling microscopy. H2Pc is adsorbed with its center over the sodium cation, and H-N bonds in the molecule are aligned with the [100] or [010] surface direction of a bilayer (001)-terminated NaCl film. The most stable structures of MgPc on the NaCl film show two kinds of orientations corresponding to the molecule rotated by ±7∘ relative to the [110] surface direction, with the Mg cation positioned over the chlorine anion in both cases. The energetic barrier for switching between these orientations is as low as 9.0 meV, and during an STM measurement, an orientational change of MgPc can be observed. The interaction between the adsorbed molecule and the NaCl film were analyzed in terms of dispersion interaction, Mg-Cl chemical bonding, and electrostatic interaction. It is found that the small electrostatic interaction between the molecule and the film gives a dominant contribution to determining the molecular orientation. Our detailed and comprehensive studies of the molecule-insulator interaction will provide knowledge to understand and control the properties of molecules on an insulating material.

  18. Shock-wave processing of C60 in hydrogen

    NASA Astrophysics Data System (ADS)

    Biennier, L.; Jayaram, V.; Suas-David, N.; Georges, R.; Singh, M. Kiran; Arunan, E.; Kassi, S.; Dartois, E.; Reddy, K. P. J.

    2017-02-01

    Context. Interstellar carbonaceous particles and molecules are subject to intense shocks in astrophysical environments. Shocks induce a rapid raise in temperature and density which strongly affects the chemical and physical properties of both the gas and solid phases of the interstellar matter. Aims: The shock-induced thermal processing of C60 particles in hydrogen has been investigated in the laboratory under controlled conditions up to 3900 K with the help of a material shock-tube. Methods: The solid residues generated by the exposure of a C60/H2 mixture to a millisecond shock wave were collected and analyzed using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman micro-spectroscopy, and infrared micro-spectroscopy. The gaseous products were analyzed by Gas Chromatography and Cavity Ring Down Spectroscopy. Results: Volatile end-products appear above reflected shock gas temperatures of 2540 K and reveal the substantial presence of small molecules with one or two C atoms. These observations confirm the role played by the C2 radical as a major product of C60 fragmentation and less expectedly highlight the existence of a single C atom loss channel. Molecules with more than two carbon atoms are not observed in the post-shock gas. The analysis of the solid component shows that C60 particles are rapidly converted into amorphous carbon with a number of aliphatic bridges. Conclusions: The absence of aromatic CH stretches on the IR spectra indicates that H atoms do not link directly to aromatic cycles. The fast thermal processing of C60 in H2 over the 800-3400 K temperature range leads to amorphous carbon. The analysis hints at a collapse of the cage with the formation of a few aliphatic connections. A low amount of hydrogen is incorporated into the carbon material. This work extends the range of applications of shock tubes to studies of astrophysical interest.

  19. High resolution 13C NMR investigation of A6C 60 ( A=K, Rb, Cs) and Ba 3C 60

    NASA Astrophysics Data System (ADS)

    Hajji, L.; Rachdi, F.; Goze, C.; Mehring, M.; Fischer, J. E.

    1996-11-01

    We report the result of 13C nuclear magnetic resonance (NMR) measurements on A6C 60 ( A=K, Rb, Cs) and Ba 3C 60. By using high-resolution magic angle spinning, we were able to identify an isotropic line around 156 ppm for all investigated compounds. NMR spectra of the saturated alkali compounds are quite similar. The corresponding isotropic lines show three narrow components consistent with orientationally ordered C 60 molecules leading to three non-equivalent carbon sites in these compounds as reported by x-ray studies. No line splitting was observed for the Ba 3C 60 isotropic line.

  20. Adsorbed Molecules and Surface Treatment Effect on Optical Properties of ZnO Nanowires Grown by MOCVD

    NASA Astrophysics Data System (ADS)

    Jabri, S.; Souissi, H.; Sallet, V.; Lusson, A.; Meftah, A.; Galtier, P.; Oueslati, M.

    2017-07-01

    We have investigated the optical properties of ZnO nanowires grown by metalorganic chemical vapor deposition (MOCVD) with nitrous oxide (N2O) as oxygen precursor. Photoluminescence (PL) and Raman measurements showed the influence of adsorbed molecules on the optical properties. Low-temperature (4 K) PL studies on the surface exciton (SX) at 3.3660 eV elucidated the nature and origin of this emission. In particular, surface treatment by annealing at high temperature under inert gas reduced the emission intensity of SX. Raman vibrational spectra proved that presence of a considerable amount of adsorbed molecules on the surface of ZnO nanowires plays a key role in the occurrence of surface excitons.

  1. Infrared-Laser Excitation of the Internal Vibrational Mode of a Diatomic Molecule Adsorbed on a Metal Surface.

    DTIC Science & Technology

    1986-11-01

    Excitation of the Internal Vibrational Mode of a Diatomic Molecule Adsorbed on a Metal Surface m by ’ Andre Peremans, Jacques Darville , Jean-Marie...Andre Peremans, Jacques Darville , Jean-Marie Gilles and Thomas F. George 13. TYPE OF REPORT 13b. TIME COVERED 14. DATE OF REPORT (Yr. Mo.. Dayl As...ON A METAL SURFACE h Andr& Peremans , Jacques Darville and Jean-Marie Gilles _ _ _ _ Laboratoire de Spectroscopie Mol6culaire de Surface Accesnion

  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. Mechanism of complexation of the phenothiazine dye methylene blue with fullerene C60

    NASA Astrophysics Data System (ADS)

    Buchelnikov, A. S.; Kostyukov, V. V.; Yevstigneev, M. P.; Prylutskyy, Yu. I.

    2013-04-01

    The complexation of fullerene C60 with the aromatic dye methylene blue (MB) in aqueous solution was studied. Spectrophotometric titration revealed a reasonably strong interaction between C60 and MB molecules with an equilibrium constant K = 2110 L/mol and the binding of up to five dye molecules with the surface of C60. The energy analysis of the MB-C60 system showed that the intermolecular and hydrophobic interactions were dominant in the energy profile of the complexation, and while the electrostatic factor played an insignificant role.

  4. 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

  5. Complexation of C60 fullerene with aromatic drugs.

    PubMed

    Evstigneev, Maxim P; Buchelnikov, Anatoly S; Voronin, Dmitry P; Rubin, Yuriy V; Belous, Leonid F; Prylutskyy, Yuriy I; Ritter, Uwe

    2013-02-25

    The contributions of various physical factors to the energetics of complexation of aromatic drug molecules with C(60) fullerene are investigated in terms of the calculated magnitudes of equilibrium complexation constants and the components of the net Gibbs free energy. Models of complexation are developed taking into account the polydisperse nature of fullerene solutions in terms of the continuous or discrete (fractal) aggregation of C(60) molecules. Analysis of the energetics has shown that stabilization of the ligand-fullerene complexes in aqueous solution is mainly determined by intermolecular van der Waals interactions and, to lesser extent, by hydrophobic interactions. The results provide a physicochemical basis for a potentially new biotechnological application of fullerenes as modulators of biological activity of aromatic drugs.

  6. Near-IR Photoluminescence of C60().

    PubMed

    Strelnikov, Dmitry V; Kern, Bastian; Kappes, Manfred M

    2017-10-05

    We have observed that C60(+) ions isolated in cryogenic matrices show distinct near-IR photoluminescence upon excitation in the near-IR range. By contrast, UV photoexcitation does not lead to measurable luminescence. Near-IR C60(+) photoluminescence is a one-photon process. The emission is mainly concentrated in one band and corresponds to (2)A1u ← (2)E1g relaxation. We present experimental data for the Stokes shift, power, and temperature dependencies as well as the quantum efficiency of the photoluminescence. Our findings may be relevant for astronomy, considering recent unequivocal assignment of five diffuse interstellar bands to near-IR absorption bands of C60(+).

  7. Resonant core spectroscopies of the charge transfer interactions between C60 and the surfaces of Au(111), Ag(111), Cu(111) and Pt(111)

    NASA Astrophysics Data System (ADS)

    Gibson, Andrew J.; Temperton, Robert H.; Handrup, Karsten; O'Shea, James N.

    2017-03-01

    Charge transfer interactions between C60 and the metal surfaces of Ag(111), Cu(111), Au(111) and Pt(111) have been studied using synchrotron-based photoemission, resonant photoemission and X-ray absorption spectroscopies. By placing the X-ray absorption and valence band spectra on a common binding energy scale, the energetic overlap of the unoccupied molecular orbitals with the density of states of the underlying metal surface have been assessed in the context of possible charge transfer pathways. Resonant photoemission and resonant Auger data, measuring the valence region as a function of photon energy for C60 adsorbed on Au(111) reveals three constant high kinetic energy features associated with Auger-like core-hole decay involving an electron transferred from the surface to the LUMO of the molecule and electrons from the three highest occupied molecular orbitals, respectively and in the presence of ultra-fast charge transfer of the originally photoexcited molecule to the surface. Data for the C60/Ag(111) surface reveals an additional Auger-like feature arising from a core-hole decay process involving more than one electron transferred from the surface into the LUMO. An analysis of the relative abundance of these core-hole decay channels estimates that on average 2.4 ± 0.3 electrons are transferred from the Ag(111) surface into the LUMO. A core-hole clock analysis has also been applied to assess the charge transfer coupling in the other direction, from the molecule to the Au(111) and Ag(111) surfaces. Resonant photoemission and resonant Auger data for C60 molecules adsorbed on the Pt(111) and Cu(111) surfaces are shown to exhibit no super-Auger features, which is attributed to the strong modification of the unoccupied molecular orbitals arising from stronger chemical coupling of the molecule to the surface.

  8. Modelling the manipulation of C60 on the Si001 surface performed with NC-AFM.

    PubMed

    Martsinovich, N; Kantorovich, L

    2009-04-01

    We present a theoretical model of manipulation of the C(60) molecule on the Si(001) surface with a non-contact atomic force microscope (NC-AFM). The model relies on the lowering of the energy barrier for the C(60) manipulation due to the interaction of the C(60) with an AFM tip and the subsequent thermal movement of the molecule over this barrier. We performed numerical simulations of these energy barriers for a series of tip positions relative to the molecule to show how the barriers change with the tip position. The values of these barriers are then used in kinetic Monte Carlo simulations to estimate the probability of the C(60) movement for different tip positions and temperatures. Virtual atomic force microscope simulations, which include the kinetic Monte Carlo treatment of the C(60) movement, are then performed to describe in real time the process of movement of the C(60) molecule during an NC-AFM scan. Our results demonstrate that manipulation of the C(60) molecule, which is covalently bound to the surface, is possible with NC-AFM, even though there is no continuous tip-molecule contact, which is known to be a necessary requirement for the C(60) manipulation with scanning tunnelling microscopy. We show that the manipulation event can be identified in real NC-AFM experiments as an abrupt change in the distance of the tip closest approach (topography), and as spikes in the frequency shift and dissipation signals.

  9. Continuous symmetry of C60 fullerene and its derivatives.

    PubMed

    Sheka, E F; Razbirin, B S; Nelson, D K

    2011-04-21

    Conventionally, the I(h) symmetry of fullerene C(60) is accepted, which is supported by numerous calculations. However, this conclusion results from the consideration of the molecule electron system, of its odd electrons in particular, in a closed-shell approximation without taking the electron spin into account. Passing to the open-shell approximation has led to both the energy and the symmetry lowering up to C(i). Seemingly contradicting to a high-symmetry pattern of experimental recording, particularly concerning the molecule electronic spectra, the finding is considered in this Article from the continuous symmetry viewpoint. Exploiting continuous symmetry measure and continuous symmetry level approaches, it was shown that formal C(i) symmetry of the molecule is by 99.99% I(h). A similar continuous symmetry analysis of the fullerene monoderivatives gives a reasonable explanation of a large variety of their optical spectra patterns within the framework of the same C(1) formal symmetry exhibiting a strong stability of the C(60) skeleton. TOC color pictures present chemical portrait of C(60) in terms of atomic chemical susceptibility (Sheka, E. Fullerenes: Nanochemistry, Nanomagnetism, Nanomedicine, Nanophotonics; CRC Press: Taylor and Francis Group, Boca Raton, 2011).

  10. Sublimation of hydrofullerenes C 60H 36 and C 60H 18

    NASA Astrophysics Data System (ADS)

    Dorozhko, P. A.; Lobach, A. S.; Popov, A. A.; Senyavin, V. M.; Korobov, M. V.

    2001-03-01

    Thermal behavior of two hydrofullerenes, C 60H 36 and C 60H 18, was studied by means of Knudsen cell mass-spectrometry and infrared spectroscopy. Vapor pressures and enthalpies of sublimation at T=550-685 K were measured. Sublimation of the hydrofullerenes was accompanied by partial loss of hydrogen. Decomposition of C 60H 36 was confirmed to be a stepwise process with formation of C 60H 18 as an intermediate product. The material of the Knudsen cell strongly affected the partial pressures and mass-spectra of the hydrofullerene vapor species.

  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. 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.

  13. Temperature Evolution of Quasi-one-dimensional C60 Nanostructures on Rippled Graphene.

    PubMed

    Chen, Chuanhui; Zheng, Husong; Mills, Adam; Heflin, James R; Tao, Chenggang

    2015-09-22

    We report the preparation of novel quasi-one-dimensional (quasi-1D) C60 nanostructures on rippled graphene. Through careful control of the subtle balance between the linear periodic potential of rippled graphene and the C60 surface mobility, we demonstrate that C60 molecules can be arranged into a quasi-1D C60 chain structure with widths of two to three molecules. At a higher annealing temperature, the quasi-1D chain structure transitions to a more compact hexagonal close packed quasi-1D stripe structure. This first experimental realization of quasi-1D C60 structures on graphene may pave a way for fabricating new C60/graphene hybrid structures for future applications in electronics, spintronics and quantum information.

  14. Temperature Evolution of Quasi-one-dimensional C60 Nanostructures on Rippled Graphene

    PubMed Central

    Chen, Chuanhui; Zheng, Husong; Mills, Adam; Heflin, James R.; Tao, Chenggang

    2015-01-01

    We report the preparation of novel quasi-one-dimensional (quasi-1D) C60 nanostructures on rippled graphene. Through careful control of the subtle balance between the linear periodic potential of rippled graphene and the C60 surface mobility, we demonstrate that C60 molecules can be arranged into a quasi-1D C60 chain structure with widths of two to three molecules. At a higher annealing temperature, the quasi-1D chain structure transitions to a more compact hexagonal close packed quasi-1D stripe structure. This first experimental realization of quasi-1D C60 structures on graphene may pave a way for fabricating new C60/graphene hybrid structures for future applications in electronics, spintronics and quantum information. PMID:26391054

  15. A discrete interaction model/quantum mechanical method for describing response properties of molecules adsorbed on metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Morton, Seth Michael; Jensen, Lasse

    2010-08-01

    A new polarizable quantum mechanics/molecular mechanics method for the calculation of response properties of molecules adsorbed on metal nanoparticles is presented. This method, which we denote the discrete interaction model/quantum mechanics (DIM/QM) method, represents the nanoparticle atomistically which enables the modeling of the influence of the local environment of a nanoparticle surface on the optical properties of a molecule. Using DIM/QM, we investigate the excitation energies of rhodamine-6G (R6G) and crystal violet (CV) adsorbed on silver and gold nanoparticles of different quasispherical shapes and sizes. The metal nanoparticle is characterized by its static total polarizability, a reasonable approximation for frequencies far from the plasmon resonance. We observe that for both R6G and CV, the presence of the nanoparticle shifts the strongest excitation to the red ˜40 nm and also increases the oscillator strength of that excitation. The shifts in excitation energies due to the nanoparticle surface are found to be comparable to those due to solvation. We find that these shifts decay quickly as the molecule is moved away from the surface. We also find that the wavelength shift is largest when the transition dipole moment is aligned with the edges of the nanoparticle surface where the electric field is expected to be the largest. These results show that the molecular excitations are sensitive to the local environment on the nanoparticle as well as the specific orientation of the molecule relative to the surface.

  16. Pentaindenocorannulene: Properties, Assemblies, and C60 Complex.

    PubMed

    Lampart, Samuel; Roch, Loïc M; Dutta, Amit K; Wang, Yujia; Warshamanage, Rangana; Finke, Aaron D; Linden, Anthony; Baldridge, Kim K; Siegel, Jay S

    2016-11-14

    Pentaindenocorannulene (C50 H20  , 1), a deep bowl polynuclear aromatic hydrocarbon, accepts 4 electrons, crystallizes in columnar bowl-in-bowl assemblies and forms a nested C60 @12 complex. Spectra, structures and computations are presented. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. High pressure infrared spectroscopy study on C60∗CS2 solvates

    NASA Astrophysics Data System (ADS)

    Du, Mingrun; Zhou, Miao; Yao, Mingguang; Ge, Peng; Chen, Shuanglong; Yang, Xigui; Liu, Ran; Liu, Bo; Cui, Tian; Sundqvist, Bertil; Liu, Bingbing

    2017-02-01

    High pressure IR study has been carried out on C60∗CS2 solvates up to 34.8 GPa. It is found that the intercalated CS2 molecules significantly affect the transformations of C60 molecules under pressure. As a probe, the intercalated CS2 molecules can well detect the orientational ordering transition and deformation of C60 molecules under pressure. The chemical stability of CS2 molecules under pressure is also dramatically enhanced due to the spacial shielding effet from C60 molecules around in the solvated crystal. These results provide new insight into the effect of interactions between intercalants and fullerenes on the transformations in fullerene solvates under pressure.

  18. Density functional study of reactivity and regioselectivity of H2O C60

    NASA Astrophysics Data System (ADS)

    KC, Govinda Bahadur

    The exohedral reactivity of endohedral fullerene has aroused significant interest because of its potential applications in biology, medicine and material science. The encapsulation of a single water molecule without any hydrogen bonding to other compounds, inside the hydrophobic environment of C60 is an intriguing topic to study about. In 2011, Kurotobi and Murata successfully synthesized H2O C60 fullerene. The presence of a polar water molecule inside the cage is expected to cause changes in the exohedral reactivity of C60. In order to find out the impact of an entrapped single water molecule on the reactivity of C60 fullerene, we use density functional theory to study the thermodynamics and kinetics of [4+2] Diels-Alder reaction of 1, 3 cis butadiene at all non-identical bonds of free C60 and H2O C60. Our calculations show that the encapsulation of a single water molecule does not have any significant effect on the exohedral reactivity compared to free C60. Moreover, the obtained reaction energies and activation barriers indicate that [6, 6] bond is more reactive than [5, 6] bond and thus cycloaddition is clearly favored at [6, 6] bond. The dipole moment of the H2O C60 is only 0.48 Debye significantly smaller than that of water molecule. The infrared and Raman spectra of the endohedral fullerene are also computed.

  19. Heat capacity measurements of atoms and molecules adsorbed on evaporated metal films

    SciTech Connect

    Kenny, T.W.

    1989-05-01

    Investigations of the properties of absorbed monolayers have received great experimental and theoretical attention recently, both because of the importance of surface processes in practical applications such as catalysis, and the importance of such systems to the understanding of the fundamentals of thermodynamics in two dimensions. We have adapted the composite bolometer technology to the construction of microcalorimeters. For these calorimeters, the adsorption substrate is an evaporated film deposited on one surface of an optically polished sapphire wafer. This approach has allowed us to make the first measurements of the heat capacity of submonolayer films of /sup 4/He adsorbed on metallic films. In contrast to measurements of /sup 4/He adsorbed on all other insulating substrates, we have shown that /sup 4/He on silver films occupies a two-dimensional gas phase over a broad range of coverages and temperatures. Our apparatus has been used to study the heat capacity of Indium flakes. CO multilayers, /sup 4/He adsorbed on sapphire and on Ag films and H/sub 2/ adsorbed on Ag films. The results are compared with appropriate theories. 68 refs., 19 figs.

  20. Electronic contributions to infrared spectra of adsorbate molecules on metal surfaces: Ethene on Cu(1 1 1)

    NASA Astrophysics Data System (ADS)

    Skibbe, O.; Binder, M.; Otto, A.; Pucci, A.

    2008-05-01

    Already at coverages well below 1 ML copper ad-atoms on Cu(1 1 1) significantly modify infrared reflection-absorption spectra of ethene (C2H4) on Cu(1 1 1). Raman modes of the centrosymmetric molecule appear in the spectra. Their lines do not involve significant shifts of vibration frequencies as they would be expected for strong distortions of the molecule. High-resolution electron-energy-loss spectra of adsorbed ethene for various Cu-adatom precoverage show the same vibration lines. Since the molecules are obviously unchanged, the Raman lines in the infrared spectra must have obtained dynamic dipole moment from transient electron transfer favored by atomic disorder on the metal surface.

  1. The low-temperature heat capacity of fullerite C60

    NASA Astrophysics Data System (ADS)

    Bagatskii, M. I.; Sumarokov, V. V.; Barabashko, M. S.; Dolbin, A. V.; Sundqvist, B.

    2015-08-01

    The heat capacity at constant pressure of fullerite C60 has been investigated using an adiabatic calorimeter in a temperature range from 1.2 to 120 K. Our results and literature data have been analyzed in a temperature interval from 0.2 to 300 K. The contributions of the intramolecular and lattice vibrations into the heat capacity of C60 have been separated. The contribution of the intramolecular vibration becomes significant above 50 K. Below 2.3 K the experimental temperature dependence of the heat capacity of C60 is described by the linear and cubic terms. The limiting Debye temperature at T →0 K has been estimated (Θ0 = 84.4 K). In the interval from 1.2 to 30 K the experimental curve of the heat capacity of C60 describes the contributions of rotational tunnel levels, translational vibrations (in the Debye model with Θ0 = 84.4 K), and librations (in the Einstein model with ΘE,lib = 32.5 K). It is shown that the experimental temperature dependences of heat capacity and thermal expansion are proportional in the region from 5 to 60 K. The contribution of the cooperative processes of orientational disordering becomes appreciable above 180 K. In the high-temperature phase the lattice heat capacity at constant volume is close to 4.5 R, which corresponds to the high-temperature limit of translational vibrations (3 R) and the near-free rotational motion of C60 molecules (1.5 R).

  2. Rotational dynamics of confined C60 from near-infrared Raman studies under high pressure.

    PubMed

    Zou, Yonggang; Liu, Bingbing; Wang, Liancheng; Liu, Dedi; Yu, Shidan; Wang, Peng; Wang, Tianyi; Yao, Mingguang; Li, Quanjun; Zou, Bo; Cui, Tian; Zou, Guangtian; Wågberg, Thomas; Sundqvist, Bertil; Mao, Ho-Kwang

    2009-12-29

    Peapods present a model system for studying the properties of dimensionally constrained crystal structures, whose dynamical properties are very important. We have recently studied the rotational dynamics of C(60) molecules confined inside single walled carbon nanotube (SWNT) by analyzing the intermediate frequency mode lattice vibrations using near-infrared Raman spectroscopy. The rotation of C(60) was tuned to a known state by applying high pressure, at which condition C(60) first forms dimers at low pressure and then forms a single-chain, nonrotating, polymer structure at high pressure. In the latter state the molecules form chains with a 2-fold symmetry. We propose that the C(60) molecules in SWNT exhibit an unusual type of ratcheted rotation due to the interaction between C(60) and SWNT in the "hexagon orientation," and the characteristic vibrations of ratcheted rotation becomes more obvious with decreasing temperature.

  3. Structure and dynamics in self-organized C60 fullerenes.

    PubMed

    Patnaik, Archita

    2007-01-01

    This manuscript on 'structure and dynamics in self-organized C60 fullerenes' has three sections dealing with: (A) pristine C60 aggregate structure and geometry in solvents of varying dielectric constant. Here, using positronium (Ps) as a fundamental probe which maps changes in the local electron density of the microenvironment, the onset concentration for stable C60 aggregate formation and its phase behavior is deduced from the specific interactions of the Ps atom with the surrounding. (B) A novel methanofullerene dyad, based on a hydrophobic (acceptor C60 moiety)-hydrophilic (bridge with benzene and ester functionalities)-hydrophobic (donor didodecyloxybenzene) network is chosen for investigation of characteristic self-assembly it undergoes leading to supramolecular aggregates. The pi-electronic amphiphile, necessitating a critical dielectric constant epsilon > or = 30 in binary THF-water mixtures, dictated the formation of bilayer vesicles as precursors for spherical fractal aggregates upon complete dyad extraction into a more polar water phase. (C) While the molecular orientation is dependent on the packing density, the ordering of the molecular arrangement, indispensable for self-assembly depends on the balance between the structures demanded by inter-molecular and molecule-substrate interactions. The molecular orientation in a monolayer affects the orientation in a multilayer, formed on the monolayer, suggesting the possibility of the latter to act as a template for controlling the structure of the three dimensionally grown self-assembled molecular aggregation. A systematic study on the electronic structure and orientation associated with C60 functionalized aminothiol self-assembled monolayers on Au(111) surface is presented using surface sensitive Ultra-Violet Photoelectron Spectroscopy (UPS) and C-K edge Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. The results revealed drastic modifications to d-band structure of Au(111) and the

  4. Sensitivity of photoelectron diffraction to conformational changes of adsorbed molecules: Tetra-tert-butyl-azobenzene/Au(111)

    PubMed Central

    Schuler, A.; Greif, M.; Seitsonen, A. P.; Mette, G.; Castiglioni, L.; Osterwalder, J.; Hengsberger, M.

    2017-01-01

    Electron diffraction is a standard tool to investigate the atomic structure of surfaces, interfaces, and adsorbate systems. In particular, photoelectron diffraction is a promising candidate for real-time studies of structural dynamics combining the ultimate time resolution of optical pulses and the high scattering cross-sections for electrons. In view of future time-resolved experiments from molecular layers, we studied the sensitivity of photoelectron diffraction to conformational changes of only a small fraction of molecules in a monolayer adsorbed on a metallic substrate. 3,3′,5,5′-tetra-tert-butyl-azobenzene served as test case. This molecule can be switched between two isomers, trans and cis, by absorption of ultraviolet light. X-ray photoelectron diffraction patterns were recorded from tetra-tert-butyl-azobenzene/Au(111) in thermal equilibrium at room temperature and compared to patterns taken in the photostationary state obtained by exposing the surface to radiation from a high-intensity helium discharge lamp. Difference patterns were simulated by means of multiple-scattering calculations, which allowed us to determine the fraction of molecules that underwent isomerization. PMID:28217715

  5. Nonlinear optical response of C60 in solvents: picosecond transient grating experiments

    NASA Astrophysics Data System (ADS)

    Khudyakov, Dmitriy V.; Rubtsov, Igor V.; Lobach, Anatolii S.; Nadtochenko, Victor A.

    1996-05-01

    Time-resolved resonant nonlinear optical response of C60 in a chlorobenzene solution was measured for 528 nm excitation and 1055, 528, and 351 nm probing for zzzz and zzyy configurations. The slow part of the signal (8 +/- 2 ps) was attributed to the orientational motion of C60 excited molecules.

  6. In situ scanning tunneling microscopy characterization of thienothiophene-based semiconducting organic molecules adsorbed on a Au(111) electrode

    NASA Astrophysics Data System (ADS)

    Luo, Shu Rong; Chen, Sih Zih; Hsu, Ya Hua; Yau, Shueh Lin; Lin, Yu-Jou; Huang, Peng-Yi; Chen, Ming-Chou

    2013-10-01

    Organic molecules with a thienothiophene core are promising candidates for use in the fabrication of organic thin film transistors. In addition to the nature of the molecule, the adsorption orientation and spatial structure of admolecules at metal electrodes also affects the efficiency of charge injection at the molecule/metal interface. Scanning tunneling microscopy (STM), which is well-known for its sub-nanometer resolution, is particularly suitable in studying the structure of this interface. Dithieno[2,3-b:3,2-d]thiophene diphenyl (C6H5-DTT-C6H5) adsorbed on Au(111) electrode was previously examined. In this study we looked at molecules with perfluorophenyl substituents, 2-pentafluorophenyl-6-phenyldithieno[2,3-b:3‧,2‧-d]thiophene(C6F5-DTT-C6H5,1) and 2,6-bis(pentafluorophenyl)dithieno[3,2-b;2‧,3‧-d]thiophene(C6F5-DTT-C6F5, 2. In situ STM results obtained in 0.1 M HClO4 showed that these molecules could be adsorbed in ordered adlattices on a Au(111) electrode from dosing solutions made of 50 μM 1 or 2 in dicholobenzene. The adsorption strength of these molecules on Au(111) varied greatly with the electrochemical potential. They were mostly stable on Au(111) at 0.3 V (vs. reversible hydrogen electrode), but could be displaced by water dipoles and perchlorate anions at E < 0.2 V and E > 0.5 V, respectively. It was possible to take advantage of this result to improve the degree of ordering by setting the potential at 0 V briefly, then switching back to 0.3 V. While 1 was adsorbed in a lamella structure as observed previously with C6H5-DTT-C6H5, 2 was arranged in a very different structure determined largely by the need to optimize the intermolecular interactions.

  7. Rotational spectra for off-center endohedral atoms at C60 fullerene

    NASA Astrophysics Data System (ADS)

    Hernández-Rojas, J.; Bretón, J.; Gomez Llorente, J. M.

    1996-01-01

    Rotational spectra for endohedral Li+@C60 and Na+@C60 are calculated at different temperatures. Most of the features in these spectra are related with the degree of anisotropy in the atom-cage interaction. While the low anisotropy for Na+@C60 results in rather simple spectra with the 2B oscillation typical of a diatomic molecule, the more eccentric and anisotropic Li+@C60 produces complex spectra with rotational and librational bands. Some interesting effects are induced by the cage rotation, which has been incorporated through a semiclassical formalism.

  8. Thin film engineering for N@C 60 quantum computers: Spin detection and device patterning approaches

    NASA Astrophysics Data System (ADS)

    Schaefer, Sebastian; Huebener, Kati; Harneit, Wolfgang; Boehme, Christoph; Fostiropoulos, Konstantinos; Angermann, Heike; Rappich, Jörg; Behrends, Jan; Lips, Klaus

    2008-10-01

    Using pulsed electrically detected magnetic resonance (p-EDMR), we measured the coherent spin evolution of about 10,000 paramagnetic states in C 60 fullerene thin films, opening a way to study potentially single-qubit read-out mechanisms of N@C 60 molecules. The N@C 60 compatible, low-temperature method of spray-deposition of fullerenes on silicon substrates pre-patterned by local anodic oxidation is shown to yield fullerene structures on the 10 nm scale, still somewhat too coarse for quantum register structures, but suitable for further steps in the application of the p-EDMR method to N@C 60.

  9. Sorption of organic molecules on surfaces of a microporous polymer adsorbent modified with different quantities of uracil

    NASA Astrophysics Data System (ADS)

    Gus'kov, V. Yu.; Ganieva, A. G.; Kudasheva, F. Kh.

    2016-11-01

    The sorption of organic molecules on the surfaces of a number of adsorbents based on a microporous copolymer of styrene and divinylbenzene modified with different quantities of uracil is studied by means of inverse gas chromatography at infinite dilution. Samples containing 10-6, 10-5, 10-4, 10-3, 10-2, and 0.5 × 10‒1 weight parts of uracil (the pC of uracil ranges from 1.3 to 6) are studied. The contributions from different intermolecular interactions to the Helmholtz energy of sorption are calculated via the linear free energy relationship. It is found that as the concentration of uracil on the surface of the polymer adsorbent grows, the contributions from different intermolecular interactions and the conventional polarity of the surface have a bend at pC = 3, due probably to the formation of a supramolecular structure of uracil. Based on the obtained results, it is concluded that the formation of the supramolecular structure of uracil on the surface of the polymer adsorbent starts when pC < 3.

  10. Enhanced mobility of fullerene (C60) nanoparticles in the presence of stabilizing agents.

    PubMed

    Wang, Yonggang; Li, Yusong; Costanza, Jed; Abriola, Linda M; Pennell, Kurt D

    2012-11-06

    Experimental and mathematical modeling studies were performed to examine the effects of stabilizing agents on the transport and retention of fullerene nanoparticles (nC(60)) in water-saturated quartz sand. Three stabilizing systems were considered: naturally occurring compounds known to stabilize nanoparticles (Suwannee river humic acid (SRHA) and fulvic acid (SRFA)), synthetic additives used to enhance nanoparticle stability (Tween 80, a nonionic surfactant), and residual contaminants resulting from the manufacturing process (tetrahydrofuran (THF)). The results of column experiments demonstrated that the presence of THF, at concentrations up to 44.5 mg/L, did not alter nC(60) transport and retention behavior, whereas addition of SRHA (20 mg C/L), SRFA (20 mg C/L), or Tween 80 (1000 mg/L) to the influent nC(60) suspensions dramatically increased the mobility of nC(60), as demonstrated by coincidental nanoparticle and nonreactive tracer effluent breakthrough curves (BTCs) and minimal nC(60) retention. When columns were preflushed with surfactant, nC(60) transport was significantly enhanced compared to that in the absence of a stabilizing agent. The presence of adsorbed Tween 80 resulted in nC(60) BTCs characterized by a declining plateau and retention profiles that exhibited hyperexponential decay. The observed nC(60) transport and retention behavior was accurately captured by a mathematical model that accounted for coupled surfactant adsorption-desorption dynamics, surfactant-nanoparticle interactions, and particle attachment kinetics.

  11. 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.

  12. Diels-Alder addition to H2O@C60 an electronic and structural study

    NASA Astrophysics Data System (ADS)

    Reveles, J. Ulises; Govinda, K. C.; Baruah, Tunna; Zope, Rajendra R.

    2017-10-01

    Exohedral reactivity of endohedral fullerenes has aroused a significant interest because of its potential applications. The present letter examines the effect of an entrapped single water molecule on the reactivity of C60. We study the thermodynamics and kinetics of a Diels-Alder reaction occurring at all non-identical bonds of free C60 and H2O@C60. Our calculations show that encapsulation of water does not have a significant effect on H2O@C60 reactivity compared to C60, as attested by the investigation of the reaction under several orientations of H2O inside C60. Reaction and activation energies indicate that [6,6] bonds are the most reactive sites.

  13. Microscopic resolution of the interplay of Kondo screening and superconducting pairing: Mn-phthalocyanine molecules adsorbed on superconducting Pb(111)

    NASA Astrophysics Data System (ADS)

    Bauer, Johannes; Pascual, Jose I.; Franke, Katharina J.

    2013-02-01

    Magnetic molecules adsorbed on a superconductor give rise to a local competition of Cooper pair and Kondo singlet formation inducing subgap bound states. For manganese-phthalocyanine molecules on a Pb(111) substrate, scanning tunneling spectroscopy resolves pairs of subgap bound states and two Kondo screening channels. We show in a combined approach of scaling and numerical renormalization group calculations that the intriguing relation between Kondo screening and superconducting pairing is solely determined by the hybridization strength with the substrate. We demonstrate that an effective one-channel Anderson impurity model with a sizable particle-hole asymmetry captures universal and nonuniversal observations in the system quantitatively. The model parameters and disentanglement of the two screening channels are elucidated by scaling arguments.

  14. Control of the dipole layer of polar organic molecules adsorbed on metal surfaces via different charge-transfer channels

    NASA Astrophysics Data System (ADS)

    Lin, Meng-Kai; Nakayama, Yasuo; Zhuang, Ying-Jie; Su, Kai-Jun; Wang, Chin-Yung; Pi, Tun-Wen; Metz, Sebastian; Papadopoulos, Theodoros A.; Chiang, T.-C.; Ishii, Hisao; Tang, S.-J.

    2017-02-01

    Organic molecules with a permanent electric dipole moment have been widely used as a template for further growth of molecular layers in device structures. Key properties of the resulting organic films such as energy level alignment (ELA), work function, and injection/collection barrier are linked to the magnitude and direction of the dipole moment at the interface. Using angle-resolved photoemission spectroscopy (ARPES), we have systematically investigated the coverage-dependent work function and spectral line shapes of occupied molecular energy states (MESs) of chloroaluminium-phthalocyanine (ClAlPc) grown on Ag(111). We demonstrate that the dipole orientation of the first ClAlPc layer can be controlled by adjusting the deposition rate and postannealing conditions, and we find that the ELA at the interface differs by ˜0.4 eV between the Cl up and down configurations of the adsorbed ClAlPc molecules. These observations are rationalized by density functional theory (DFT) calculations based on a realistic model of the ClAlPc/Ag(111) interface, which reveal that the different orientations of the ClAlPc dipole layer lead to different charge-transfer channels between the adsorbed ClAlPc and Ag(111) substrate. Our findings provide a useful framework toward method development for ELA tuning.

  15. Doping-induced distortions and bonding in K6C60 and Rb6C60

    NASA Astrophysics Data System (ADS)

    Andreoni, Wanda; Gygi, Francois; Parrinello, Michele

    1992-02-01

    The Car-Parrinello method is here used to theoretically investigate the properties of K6C60 and Rb6C60 crystals. Results are in very good agreement with available experimental data. An interesting pattern of relaxations both in the C60 fullerene cage and in the position of the K ions with respect to an ideal configuration is noted. The relaxation energy gain is about 1 eV, and is due in comparable amounts to the C60 and the K's. These energy gains are achieved by relatively small ionic displacements. Analysis of the electronic charge density reveals non-rigid-band effects. Similarities and differences with graphite intercalation compounds are discussed.

  16. Charge-transfer photodissociation of adsorbed molecules via electron image states

    SciTech Connect

    Jensen, E. T.

    2008-01-28

    The 248 and 193 nm photodissociations of submonolayer quantities of CH{sub 3}Br and CH{sub 3}I adsorbed on thin layers of n-hexane indicate that the dissociation is caused by dissociative electron attachment from subvacuum level photoelectrons created in the copper substrate. The characteristics of this photodissociation-translation energy distributions and coverage dependences show that the dissociation is mediated by an image potential state which temporarily traps the photoelectrons near the n-hexane-vacuum interface, and then the charge transfers from this image state to the affinity level of a coadsorbed halomethane which then dissociates.

  17. Structural Energetics of Yb_2.75C_60: Charge Transfer and Local Distortions

    NASA Astrophysics Data System (ADS)

    Rabe, Karin M.; Citrin, P. H.

    1997-03-01

    The crystal structure of Yb_2.75C_60 is closely related to that of the well-known superconducting K_3C_60, but with an ordered cationic vacancy sublattice and large displacements of the Yb cations from their ideal sites.(E. Ozdas et al., Nature 375), 126 (1995). This structure is unique among known fullerene compounds in that there are crystallographically inequivalent C_60 molecules with distinct nearest-neighbor cation environments. Recent EXAFS measurements(P. H. Citrin et al., unpublished.) indicate that the C_60 molecules are also significantly distorted. Using a simple electrostatic model of Yb^2+ point cations and C_60 anions as classical charged spheres with an average charge of -5.5, we find that the structural energy is minimized by charge transfer among the inequivalent C_60 anions. The result is three different charge states of -6.2, -5.5, and -4.8. Refinements of this simple model, including charge-state- and local-field-induced distortions of the C_60 molecules and covalent bonding to the nearest-neighbor Yb cations, will be discussed. Within the model, the experimental structural data and the reasons for the stability of this structure in the Yb-C_60 system will be analyzed.

  18. On the structural distortion in Rb3C60 and K3C60 revealed by 87Rb- and39K- NMR

    NASA Astrophysics Data System (ADS)

    Apostol, M.; Goze, C.; Rachdi, F.; Mehring, M.; Fischer, J. E.

    1996-04-01

    The splitting of the tetrahedral Rb- and K- NMR lines in Rb3C60 and K3C60 is analyzed in terms of the mechanism of alkali-cation vacancies. The calculations indicate the presence of vacancies only in the tetrahedral positions, and the inter-atomic potentials between the alkali cations and the fullerene molecules account satisfactorily for the temperature dependence of the position of the distorted line.

  19. 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.

  20. Metallic properties of the ternary fullerides ABa2C60 (A=K,Rb,Cs)

    NASA Astrophysics Data System (ADS)

    Thier, K.-F.; Goze, C.; Mehring, M.; Rachdi, F.; Yildirim, T.; Fischer, J. E.

    1999-04-01

    Electronic properties and molecular dynamics of mixed alkali-alkaline earth fullerides ABa2C60 (A=K,Rb,Cs) are investigated by NMR and compared to the isostructural alkali fullerides A3C60. Consistent with previous Raman investigations, our results indicate a fivefold charge transfer to the C60, a charge state that is not found in pure alkali fullerides. 13C NMR experiments reveal a metallic ground state for all compounds with an inhomogeneous charge distribution on the fullerene molecule. The importance of electron-electron correlations is discussed in terms of the Korringa enhancement factor. Correlation effects appear to be somewhat similar to the isostructural superconducting A3C60. Transverse relaxation experiments were performed to probe the reorientational dynamics of the C60 molecules. No dependence of the activation energy of the reorientational motion on the type of alkali ion is found.

  1. Morphological investigation of Mn12 single-molecule magnets adsorbed on Au(111).

    PubMed

    Otero, Gonzalo; Evangelio, Emi; Rogero, Celia; Vázquez, Luis; Gómez-Segura, Jordi; Gago, José Angel Martín; Ruiz-Molina, Daniel

    2009-09-01

    We report on the adsorption of Mn(12) single-molecule magnets bearing external biphenyl groups on Au(111) surfaces after a simple dipping procedure. Topographic AFM images confirm that the biphenyl groups favor the adsorption of the molecules without the need of functionalization with thiols or thioether groups. The first formed molecular layer covers homogenously the whole surface, whereas further growth takes place mostly in the form of molecular wires (or aggregates) and, occasionally, as molecular islands. Interestingly, the Mn(12) core is preserved for all the cases, although its aggregation state appears to influence significantly the rigidity of the molecular aggregates. Force-volume imaging experiments have demonstrated that molecules at the second layer are stiffer, that is, more rigid, than the molecules lying at the background layer. This fact clearly reveals that the interplay of attractive and repulsive forces between molecules and the molecule-surface interaction modulate the mechanical properties of the Mn(12) single-molecule magnets upon grafting. These results are very important to understand how surface-induced morphological deformations can modify the magnetic properties of these molecular systems on the translation from the macroscopic to a surface.

  2. A coarse-grained method based on the analysis of short molecular dynamics trajectories for the simulation of non-Markovian dynamics of molecules adsorbed in microporous materials.

    PubMed

    Pintus, Alberto M; Gabrieli, Andrea; Pazzona, Federico G; Demontis, Pierfranco; Suffritti, Giuseppe B

    2014-08-21

    We developed a coarse-grained model suitable for the study of adsorbed molecules in microporous materials. A partition of the space available to the motion of adsorbed molecules was carried out, which allows to formulate the dynamics in terms of jumps between discrete regions. The probabilities of observing given pairs of successive jumps were calculated from Molecular Dynamics (MD) simulations, performed on small systems, and used to drive the motion of molecules in a lattice-gas model. Dynamics is thus reformulated in terms of event-space dynamics and this allows to treat the system despite its inherent non markovity. Despite the assumptions enforced in the algorithm, results show that it can be applied to various spherical molecules adsorbed in the all-silica zeolite ITQ-29, establishing a suitable direct bridge between MD simulation results and coarse-grained models.

  3. First principles study on the electronic transport properties of C60 and B80 molecular bridges

    NASA Astrophysics Data System (ADS)

    Zheng, X. H.; Hao, H.; Lan, J.; Wang, X. L.; Shi, X. Q.; Zeng, Z.

    2014-08-01

    The electronic transport properties of molecular bridges constructed by C60 and B80 molecules which have the same symmetry are investigated by first principles calculations combined with a non-equilibrium Green's function technique. It is found that, like C60, monomer B80 is a good conductor arising from the charge transfer from the leads to the molecule, while the dimer (B80)2 and (C60)2 are both insulators due to the potential barrier formed at the molecule-molecule interface. Our further study shows that, although both the homogeneous dimer (B80)2 and (C60)2 display poor conductivity, the heterogeneous dimer B80C60 shows a very high conductance as a result from the decreased HOMO-LUMO gap and the excess charge redistribution. Finally, we find that the conductivity of both (B80)2 and (C60)2 can be significantly improved by electron doping, for example, by doping C in (B80)2 and doping N in (C60)2.

  4. Effects of humic and fulvic acids on aggregation of aqu/nC60 nanoparticles.

    PubMed

    Zhang, Wei; Rattanaudompol, U-Sa; Li, Hui; Bouchard, Dermont

    2013-04-01

    Aggregation of fullerene nanoparticles (nC(60)) is a fundamental process influencing its environmental fate and transport, and toxicity. Using time-resolved dynamic light scattering we systematically investigated aggregation kinetics of nC(60) generated from extended mixing in water (termed as aqu/nC(60)) in a range of symmetrical monovalent (NaCl) or divalent (MgSO(4)) electrolyte concentrations with the presence/absence of model natural organic matter (NOM), i.e., Suwannee River humic acid (SRHA) and fulvic acid (SRFA), at three pH levels (4, 7.8, 9.8). Electrophoretic mobility (EPM) data were interpreted according to the Ohshima's soft particle theory to obtain average characteristics of the adsorbed NOM layers, which was then used to explain the observed aggregation profiles. Results indicate that the presence of NOM stabilized aqu/nC(60), and SRHA was more effective than SRFA in suppressing aqu/nC(60) aggregation. The stabilization effect of NOM in the presence of NaCl was less pronounced than in the presence of MgSO(4), likely as a result of high aggregation potential of aqu/nC(60) in the presence of MgSO(4) due to effective charge screening and neutralization. The differential stabilization capacity between SRHA and SRFA could be explained by the structural and conformational characteristics of the adsorbed NOM layers by invoking steric repulsion, as determined by both the adsorbed layer thickness and the NOM affinity to aqu/nC(60). While this was true under most conditions, the discrepancy observed in the presence of MgSO(4) at pH 9.8 may be attributed to inter-particle aggregation through Mg(2+) binding with SRFA that is not included in steric repulsion theory. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Preparation and surface enhanced Raman scattering behavior of Ag-coated C60 nanoclusters

    NASA Astrophysics Data System (ADS)

    Kang, Shi-Zhao; Yin, Die-er; Li, Xiangqing; Mu, Jin

    2013-12-01

    Ag-coated C60 nanoclusters were prepared and characterized with X-ray diffraction, transmission electron microscopy and nitrogen adsorption-desorption isotherm measurement. The Ag-coated C60 nanoclusters were assembled on the glass substrate to form a thin film using the layer-by-layer technique. Meanwhile, the surface enhanced Raman scattering (SERS) of musk xylene adsorbed on the film of Ag-coated C60 nanoclusters was explored. The results indicated that the film of Ag-coated C60 nanoclusters was a unique SERS-active substrate with a detection limit of 10-9 mol L-1 for musk xylene. Furthermore, the surface enhanced mechanisms were discussed preliminarily.

  6. Global minima of (C 60) nCa 2+, (C 60) nF - and (C 60) nI - clusters

    NASA Astrophysics Data System (ADS)

    Hernández-Rojas, J.; Bretón, J.; Llorente, J. M. Gomez; Wales, D. J.

    2005-07-01

    Likely candidates for the lowest potential energy minima of (C 60) nCa 2+, (C 60) nF - and (C 60) nI - clusters are located using basin-hopping global optimisation. In each case, the potential energy surface is constructed using the Girifalco form for the C 60 intermolecular interaction, an averaged Lennard-Jones C 60-ion interaction, and a polarisation potential, which depends on the first few non-vanishing C 60 multipole polarisabilities. We find that the ions generally occupy the interstitial sites of a (C 60) n cluster, the coordination shell being tetrahedral for Ca 2+ and F -. The I - ion has an octahedral coordination shell in the global minimum for (C 60) 6I -, however for 12 ⩾ n ⩾ 8 the preferred coordination geometry is trigonal prismatic.

  7. Impurity Decoration for Crystal Shape Control: C60 on Ag(111)

    NASA Astrophysics Data System (ADS)

    Stasevich, T. J.; Tao, C. G.; Cullen, W. G.; Williams, E. D.; Einstein, T. L.

    2008-03-01

    The decoration of hexagonal Ag/Ag(111) monolayer islands by chains of C60, observed via STM at 300K, dramatically changes their shape and fluctuations. We tune coverage so that a single C60 chain fully decorates each Ag island boundary.ootnotetextC.G. Tao et al., PRB 73, 125436 (2006); Nano Letters 7, 1495 (2007). The C60-induced rounding appears due to competing energetic and entropic effects.ootnotetextT.J. Stasevich & TLE, (SIAM) Multiscale Model. Simul. 6, 90 (2007) We estimate the Ag - C60 and C60 - C60 attractions as ˜0.13 eV and ˜0.04 eV, respectively.ootnotetextT.J. Stasevich et al., submitted. The edge fluctuations are remarkable: 1) C60 decoration does not notably impede the step-edge diffusion (SED) and 2) while the bare-island fluctuations are driven by SED, the decorated island has the signature of non-conserved dynamics, even though the C60s remain at the island edge. We suggest that rapidly diffusing Ag atoms randomly attracting the nearby C60s. Generalizations of our model show that both spherical and rectangular decorating molecules will similarly lower the energy of highly-kinked boundaries, leading to similar island shape changes.

  8. Spectroscopic studies of the interaction of C 60 and C 70 films with metal substrates

    NASA Astrophysics Data System (ADS)

    Zhao, Wei; Chen, Li-Quan; Li, Yu-Xin; Zhao, Tie-Nan; Huang, Yu-Zhen; Zhang, Zhan-Xiang; Wang, Hui-Tian; Ye, Pei-Xian; Zhao, Zhong-Xian

    1994-09-01

    The interaction of fullerenes C 60 and C 70 films with metal substrates Au, Ag, In and Sn has been studied by UV-visible absorption spectra, IR, Raman, photoluminescence and second-order nonlinear optics. The absorption spectra show new bands for films on Au, Ag, In and Sn film substrates. For C 60 on Au and Ag, new bands appear, peaking at 723 and 566 nm, respectively. For C 60 film on Sn, several new bands are found at 975.4, 1218, 1557, 2000 and 3570 nm in the NIR and IR regions. Raman spectra reveal an additional peak at 350 cm-1 for C 60 film on Au and five new peaks at 350, 532, 564, 1692 and 1850 cm-1 for the film on Sn. An enhancement of the Raman peak intensity is observed in the latter case. A peak blue shift of photoluminescence band from 749 to 735 nm for C 60 on Sn has also been found. Moreover, a second-order nonlinear optics study at 1.06,μm yields a ten times greater secondary harmonic generation signal intensity for C 60 films on Ag than that of Ag, while no signal is observed for C 60 film on glass. For C 70 on Sn, UV absorption bands broaden and new bands are found at 747, 984 and 1738 nm. The above results suggest a structural distortion of C 60 and C 70 molecules, induced by charge transfer from these metals to the molecules.

  9. Optical High Harmonic Generation in C60

    NASA Astrophysics Data System (ADS)

    Zhang, Guoping

    2005-03-01

    C60 et al. Physical Review Letters Physical Review B High harmonic generation (HHG) requires a strong laser field, but in a relatively weak laser field is sufficient. Numerical results presented here show while its low order harmonics result from the laser field, its high order ones are mainly from the multiple excitations. Since high order harmonics directly correlate electronic transitions, the HHG spectrum accurately measures transition energies. Therefore, is not only a promising material for HHG, but may also present an opportunity to develop HHG into an electronic structure probing tool. References: G. P. Zhang, 91, 176801 (2003); G. P. Zhang and T. F. George, 68, 165410 (2003); P. B. Corkum, 71, 1994 (1993); G. P. Zhang and Thomas F. George, 93, 147401 (2004); H. Niikura ,ature 417, 917 (2002); ibid. 421, 826 (2003); Y. Mairesse ,cience 302, 1540 (2003); A. Baltuska ,ature 421, 611 (2003).

  10. Antiferromagnetic resonance in Rb1C60

    NASA Astrophysics Data System (ADS)

    Bennati, M.; Griffin, R. G.; Knorr, S.; Grupp, A.; Mehring, M.

    1998-08-01

    High-frequency (94 and 140 GHz) ESR was used to investigate the magnetic properties of the low-dimensional conductor Rb1C60. Below 35 K new features of the electron spin resonance are distinguished from the CESR signal of the conducting phase. The analysis of the resonance linewidth and line shift allows a clear identification of a frequency-dependent antiferromagnetic resonance line (AFMR) below 25 K. The characteristic temperature TN for the ordering transition is 25 K. Between 25 K

  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. The adsorption of C 60 and the co-adsorption of C 60 and H 2O on α-Al 2O 3 (1 overline102)-(2 × 1)

    NASA Astrophysics Data System (ADS)

    Hamza, A. V.; Balooch, M.

    1992-10-01

    Binding of submonolayer coverages of C 60 to α-Al 2O 3(1 overline102)-(2 × 1) is observed by temperature-programmed desorption with peak temperatures for desorption between 430 and 460 K. Estimated first-order activation energy and pre-exponential factor are 25 ± 6 kcal/mol and 6.3 × 10 11 s -1. Multilayer desorption of C 60 behaves similarly to that observed previously from the (0001) surface. Exposure of C 60 to a water pre-dosed surface did not displace the adsorbed surface hydroxyls. Concomitant desorption of C 60 and water is observed from a water pre-dosed surface subsequently exposed to C 60 multilayers, whereas water post-dosed onto a C 60-covered surface has a sticking probability less than 4 × 10 -3.

  13. Effects of non-local exchange on core level shifts for gas-phase and adsorbed molecules

    NASA Astrophysics Data System (ADS)

    Van den Bossche, M.; Martin, N. M.; Gustafson, J.; Hakanoglu, C.; Weaver, J. F.; Lundgren, E.; Grönbeck, H.

    2014-07-01

    Density functional theory calculations are often used to interpret experimental shifts in core level binding energies. Calculations based on gradient-corrected (GC) exchange-correlation functionals are known to reproduce measured core level shifts (CLS) of isolated molecules and metal surfaces with reasonable accuracy. In the present study, we discuss a series of examples where the shifts calculated within a GC-functional significantly deviate from the experimental values, namely the CLS of C 1s in ethyl trifluoroacetate, Pd 3d in PdO and the O 1s shift for CO adsorbed on PdO(101). The deviations are traced to effects of the electronic self-interaction error with GC-functionals and substantially better agreements between calculated and measured CLS are obtained when a fraction of exact exchange is used in the exchange-correlation functional.

  14. Some features of raman scattering by molecules adsorbed on metal crystal faces and a fine light structure

    NASA Astrophysics Data System (ADS)

    Polubotko, A. M.

    2013-07-01

    The paper analyzes some experiments on Raman scattering by molecules adsorbed on the face (111) of silver monocrystals performed by A. Campion et al. From the existence of the forbidden line A 2 u of benzene, the conclusion about existence of the surface field, caused by atomic structure of the surface is made. The relatively large intensity of this line allows to make a conclusion about large influence of the electromagnetic field spatial inhomogeneity in crystals on their optical properties. The difference between this field and a regular plane wave, which usually describes propagation of electromagnetic field in solids is named as a fine light structure. The influence of this structure on optical properties of solids is pointed out.

  15. Competing length scales for the electronic structure of rings of C60

    NASA Astrophysics Data System (ADS)

    Tan, Jerry; Bryant, Garnett

    Recently, rings of C60 have been fabricated. This opens up the possibility of studying the electronic structure of complex nanosystems with competing length scales: here the length scale defined by individual C60 molecules, the length scale defined by moving along the inner edge of the ring of C60s, and the length scale for the outer edge. The effects of such competing length scales could be probed with a magnetic field B. We use a tight-binding model to study these effects theoretically. Noninteracting electrons are considered. B is included with a Peierls transformation. Calculated electronic spectrum for an isolated ring of carbons, here used as a simple model for C60, is compared with spectra for rings of carbon rings. Changes in spectra due to inter-ring hopping are identified. New structure in the density of states is correlated with the spatial distribution of states in rings of rings. A magnetic field is applied to access and couple different length scales. Calculated spectra for rings of full C60 molecules are compared with the model results to highlight the effects of competing length scales in C60 rings. Results are used to suggest possible experiments for rings of C60 molecules.

  16. Reactivity and regioselectivity of noble gas endohedral fullerenes Ng@C(60) and Ng(2)@C(60) (Ng=He-Xe).

    PubMed

    Osuna, Sílvia; Swart, Marcel; Solà, Miquel

    2009-12-07

    Recently, it was shown that genuine Ng-Ng chemical bonds are present in the endohedral fullerenes Ng(2)@C(60) in the case of Ng=Xe, while it is more debatable whether a chemical bond exist for Ng=Ar and Kr. The lighter homologues with helium and neon are weakly bonded van der Waals complexes. The presence of a noble gas dimer inside the cage is expected to modify the exohedral reactivity of the C(60) cage with respect to that of free C(60). To investigate the impact of encapsulated diatomic noble gas molecules on the chemical reactivity of C(60), we analyzed the thermodynamics and the kinetics of [4+2] Diels-Alder cycloaddition of 1,3-cis-butadiene at all nonequivalent bonds in free C(60), Ng@C(60), and Ng(2)@C(60) (Ng=He, Ne, Ar, Kr, and Xe). Our BP86/TZP calculations reveal that introduction of single noble gas atoms in Ng@C(60) and noble gas dimers He(2) and Ne(2) in Ng(2)@C(60) has almost no effect on the exohedral reactivity compared to free C(60), in agreement with experimental results. In all these cases cycloaddition is clearly favored at the [6,6] bonds in the fullerene cage. For the endohedral compounds He(2)@C(60) and Ne(2)@C(60) a slight preference (by less than 2 kcal mol(-1)) for bonds closer to the C(5) symmetry axis is found. This picture changes dramatically for the endohedral compounds with heavier noble gas dimers. Encapsulation of these noble gas dimers clearly enhances the reaction, both under thermodynamic and kinetic control. Moreover, in the case of Xe(2)@C(60), addition to [6,6] and [5,6] bonds becomes equally viable. These reactivity changes in endohedral fullerenes are attributed to stabilization of the LUMO, increased fullerene strain energy, and greater compression of the encapsulated Ng(2) unit along the He to Xe series.

  17. Hindered and modulated rotational states and spectra of adsorbed diatomic molecules

    NASA Astrophysics Data System (ADS)

    Shih, Y. T.; Chuu, D. S.; Mei, W. N.

    1996-10-01

    Both vertical and horizontal adsorption configurations of a diatomic molecule were modeled as the rigid rotor with which the spatial motion was confined by a finite conical well. In addition to the polar hindering potential, a sinusoidal azimuthal modulation, which bears the local symmetry of the adsorption site, was incorporated. Eigenfunctions for different models were expressed analytically in terms of the hypergeometric functions, and eigenvalues were solved numerically. We found that the rotational energy levels exhibit oscillatory behavior when plotted as functions of the hindrance angle. This particular phenomenon was interpreted as the occurrence of resonance transmission of the rotor wave function at certain hindrance condition. We also found that the rotational levels were grouped into bands when the azimuthal modulation strength was increased. The solutions were used to calculate the rotational-state distribution of desorbed molecules, and agreement with the previous experiment was obtained.

  18. Hindered and modulated rotational states and spectra of adsorbed diatomic molecules

    SciTech Connect

    Shih, Y.T.; Chuu, D.S.; Mei, W.N.

    1996-10-01

    Both vertical and horizontal adsorption configurations of a diatomic molecule were modeled as the rigid rotor with which the spatial motion was confined by a finite conical well. In addition to the polar hindering potential, a sinusoidal azimuthal modulation, which bears the local symmetry of the adsorption site, was incorporated. Eigenfunctions for different models were expressed analytically in terms of the hypergeometric functions, and eigenvalues were solved numerically. We found that the rotational energy levels exhibit oscillatory behavior when plotted as functions of the hindrance angle. This particular phenomenon was interpreted as the occurrence of resonance transmission of the rotor wave function at certain hindrance condition. We also found that the rotational levels were grouped into bands when the azimuthal modulation strength was increased. The solutions were used to calculate the rotational-state distribution of desorbed molecules, and agreement with the previous experiment was obtained. {copyright} {ital 1996 The American Physical Society.}

  19. Enhanced Raman scattering by molecules adsorbed at the surface of colloidal spheroids

    NASA Astrophysics Data System (ADS)

    Wang, D.-S.; Kerker, M.

    1981-08-01

    Equations are derived and calculations are presented for the electrodynamic mechanism of enhanced Raman scattering by molecules at the surface of prolate and oblate spheroids in the small-particle limit. The molecules may be arbitrarily distributed; the particles may be arbitrarily oriented. Calculations are presented for a monolayer distributed over randomly oriented spheroids. The effects of particle shape are considered for Ag, Au, and Cu hydrosols. The peak enhancement moves to longer wavelengths, and in the case of Au and Cu the magnitude of the enhancement increases strikingly as the eccentricity increases. The relation between the dependence of the Raman enhancement upon excitation wavelength and the extinction spectra is discussed, including the precariousness of extrapolating such relations beyond the small-particle limit.

  20. ESR spectroscopy of the C60 cation produced by photoinduced electron transfer

    PubMed

    Dunsch; Ziegs; Siedschlag; Mattay

    2000-10-02

    In this study the existence of the C60 cation produced by photochemically induced electron transfer in the presence of different sensitising molecules is proved for the first time by using ESR spectroscopy. It is demonstrated for triphenylpyryliumtetrafluoroborate (TPP) by this spectroscopic method that the electron transfer from C60 to TPP occurs without an application of a cosensitiser. Furthermore it is shown that the addition of alcohols causes a new radical in the system C60/TPP. The stationary concentration of the C60 cation diminishes even in the presence of a cosensitiser to such a low concentration that it is not detectable by ESR spectrosopy. The spectroscopic study of the sensitiser/C60 system is also extended to the reaction products.

  1. Switching orientation of adsorbed molecules: Reverse domino on a metal surface

    NASA Astrophysics Data System (ADS)

    Braatz, C. R.; Esat, T.; Wagner, C.; Temirov, R.; Tautz, F. S.; Jakob, P.

    2016-01-01

    A thus far unknown phase of 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA) on Ag(111), characterized by an all perpendicular orientation of the planar molecules and bound to the Ag substrate through the carboxyl oxygen atoms has been identified using infrared absorption spectroscopy and scanning tunneling microscopy. Its formation process requires second layer NTCDA to squeeze into empty spaces between relaxed monolayer NTCDA molecules. Remarkably, this process causes initially parallel oriented NTCDA to likewise adopt the new, highly inclined adsorption geometry. According to our SPA-LEED and STM findings, the new phase displays a distinct long range order and shows a pronounced tendency to form 1D rows or narrow islands. We suggest that extra NTCDA preferentially transforms into the upright configuration close to existing islands and attaches to them, i.e. the transformation process proceeds in a directed and recurrent manner (reverse domino scenario). Identical processing starting with a compressed NTCDA/Ag(111) monolayer leads to a purely parallel oriented bilayer, that is, the NTCDA monolayer phase is retained and merely acts as a passive template for bilayer NTCDA. The new vertical NTCDA phase represents an unusual molecular system with π-orbitals oriented parallel to a metal surface. A substantially reduced coupling of these orbitals to Ag(111) electronic levels is conjectured, which will have a major impact on intermolecular couplings and electronically excited state lifetimes.

  2. C60 fullerene promotes lung monolayer collapse

    PubMed Central

    Barnoud, Jonathan; Urbini, Laura; Monticelli, Luca

    2015-01-01

    Airborne nanometre-sized pollutants are responsible for various respiratory diseases. Such pollutants can reach the gas-exchange surface in the alveoli, which is lined with a monolayer of lung surfactant. The relationship between physiological effects of pollutants and molecular-level interactions is largely unknown. Here, we determine the effects of carbon nanoparticles on the properties of a model of lung monolayer using molecular simulations. We simulate phase-separated lipid monolayers in the presence of a model pollutant nanoparticle, C60 fullerene. In the absence of nanoparticles, the monolayers collapse only at very low surface tensions (around 0 mN m−1). In the presence of nanoparticles, instead, monolayer collapse is observed at significantly higher surface tensions (up to ca 10 mN m−1). Collapse at higher tensions is related to lower mechanical rigidity of the monolayer. It is possible that similar mechanisms operate on lung surfactant in vivo, which suggests that health effects of airborne carbon nanoparticles may be mediated by alterations of the mechanical properties of lung surfactant. PMID:25589571

  3. Preparation and biodistribution of radiolabeled fullerene C60 nanocrystals

    NASA Astrophysics Data System (ADS)

    Nikolić, Nadežda; Vranješ-Ðurić, Sanja; Janković, Drina; Ðokić, Divna; Mirković, Marija; Bibić, Nataša; Trajković, Vladimir

    2009-09-01

    The present study describes for the first time a procedure for the radiolabeling of fullerene (C60) nanocrystals (nanoC60) with Na 125I, as well as the biodistribution of radiolabeled nanoC60 (125I-nanoC60). The solvent exchange method with tetrahydrofuran was used to make colloidal water suspensions of radiolabeled nanoC60 particles. The radiolabeling procedure with the addition of Na 125I to tetrahydrofuran during dissolution of C60 gave a higher radiochemical yield of radiolabeled nanoC60 particles in comparison to the second option, in which Na 125I was added after C60 was dissolved. Using photon correlation spectroscopy and transmission electron microscopy, 125I-nanoC60 particles were found to have a crystalline structure and a mean diameter of 200-250 nm. The 125I-nanoC60 had a particularly high affinity for human serum albumin, displaying 95% binding efficiency after 1 h. Biodistribution studies of 125I-nanoC60 in rats indicated significant differences in tissue accumulation of 125I-nanoC60 and the radioactive tracer Na 125I. The higher accumulation of radiolabeled nanoC60 was observed in liver and spleen, while accumulation in thyroid, stomach, lungs and intestines was significantly lower in comparison to Na 125I. In addition to being useful for testing the biological distribution of nanoC60, the described radiolabeling procedure might have possible applications in cancer radiotherapy.

  4. Tribochemical synthesis of nano-lubricant films from adsorbed molecules at sliding solid interface: Tribo-polymers from α-pinene, pinane, and n-decane

    NASA Astrophysics Data System (ADS)

    He, Xin; Barthel, Anthony J.; Kim, Seong H.

    2016-06-01

    The mechanochemical reactions of adsorbed molecules at sliding interfaces were studied for α-pinene (C10H16), pinane (C10H18), and n-decane (C10H22) on a stainless steel substrate surface. During vapor phase lubrication, molecules adsorbed at the sliding interface could be activated by mechanical shear. Under the equilibrium adsorption condition of these molecules, the friction coefficient of sliding steel surfaces was about 0.2 and a polymeric film was tribochemically produced. The synthesis yield of α-pinene tribo-polymers was about twice as much as pinane tribo-polymers. In contrast to these strained bicyclic hydrocarbons, n-decane showed much weaker activity for tribo-polymerization at the same mechanical shear condition. These results suggested that the mechanical shear at tribological interfaces could induce the opening of the strained ring structure of α-pinene and pinane, which leads to polymerization of adsorbed molecules at the sliding track. On a stainless steel surface, such polymerization reactions of adsorbed molecules do not occur under typical surface reaction conditions. The mechanical properties and boundary lubrication efficiency of the produced tribo-polymer films are discussed.

  5. Infrared spectroscopy of water clusters co-adsorbed with hydrogen molecules on a sodium chloride film

    NASA Astrophysics Data System (ADS)

    Yamakawa, Koichiro; Fukutani, Katsuyuki

    2016-06-01

    Hydrogen gas containing a trace of water vapor was dosed on a vacuum-evaporated sodium chloride film at 13 K, and water clusters formed on the substrate were investigated by infrared absorption spectroscopy. Absorption bands due to (H2O)n clusters with n = 3-6 and an induced absorption band due to hydrogen were clearly observed. With increasing gas dosage, the intensities of the cluster bands increased linearly while the intensity of the hydrogen band was constant. This suggests that the water clusters were formed in two-dimensional matrices of hydrogen. We found that the water clusters did exist on the surface upon heating even after the hydrogen molecules had desorbed. A further rise of the substrate temperature up to 27 K yielded the formation of larger clusters, (H2O)n with n > 6 . We also discuss the origins of the two bands of the trimer in terms of pseudorotation and a metastable isomer.

  6. Density-functional theory for the dynamical response of molecules adsorbed on metal surfaces

    NASA Astrophysics Data System (ADS)

    Gies, Peter; Gerhardts, Rolf R.

    1988-06-01

    The electromagnetic interaction between an oscillating point dipole and different metallic surfaces, described within the self-consistent jellium model, is calculated microscopically for frequencies up to the bulk plasma frequency, using the dynamical density-functional approach. For dipole-jellium distances smaller than 5 Å, the induced field at the position of the dipole is mainly determined by the nonlocal optical effects, and classical image-field theory fails completely. We further calculate the surface-induced renormalization of the molecular polarizability, which is caused by electron-hole pair and, above the surface-plasmon frequency, collective plasma excitations. The relevance of these findings for surface-enhanced Raman scattering, for adsorption of organic molecules, and for metallic impurities immediately below the surface is discussed.

  7. Sorption of nano-C60 clusters in soil: hydrophilic or hydrophobic interactions?

    PubMed

    Forouzangohar, Mohsen; Kookana, Rai S

    2011-05-01

    We studied the sorption behaviour of fullerene nano-C(60) particles (nC(60)) in soil from binary solvent mixtures of ethanol-water in order to critically evaluate the previous reports in the literature that the partitioning mechanism explains the soil sorption of fullerene C(60) as hydrophobic molecules. The sorption of nC(60) particles was studied in a range of solvent mixtures by changing volume fractions of ethanol from 20 to 100 percent. Sorption and particle characteristics were found to be very different in ethanol : water mixtures above and below 60% ethanol. In the range of 20-60% ethanol, sorption increased from 1.2 to 14.6 L kg(-1) accompanied by a change in zeta (ζ) potential from -32.4 to -7.2 mV. This observation can be attributed to hydrophilic interactions that negatively charged nC(60) particles undergo with soil colloids and water molecules. From 60% to 100% ethanol volume fractions, hydrophobic interactions of weakly charged nanoparticles may control the overall extent of soil sorption. The findings of this study indicate the importance of hydrophilic forces in controlling the sorption behaviour of nC(60) particles which are stabilized in water dominated solvent mixtures. The validity of the partitioning mechanism and K(OC) modelling approach in describing and estimating the sorption of nC(60) particles in soil (previously suggested in the literature) are, therefore, questioned.

  8. Azafullerene C 59N, a stable free radical substituent in crystalline C 60

    NASA Astrophysics Data System (ADS)

    Fülöp, Ferenc; Rockenbauer, Antal; Simon, Ferenc; Pekker, Sándor; Korecz, László; Garaj, Slaven; Jánossy, András

    2001-02-01

    Solid solutions of C 59N azafullerene in C 60 with concentrations of 10 -5 to 10 -4 were produced in large quantities in an electric gas discharge tube. C 59N is a stable monomeric substituent molecule in crystalline C 60. The isotropic 14N and 13C hyperfine coupling constants measured by electron spin resonance (ESR) are characteristic of the extent of delocalization of the charge over the cage and are a sensitive test of electronic structure calculations. The C 59N reorientational activation energy measured below the face centered cubic (fcc) to simple cubic (sc) transition is 2300 K. This value is similar to that of the matrix C 60 molecules, indicating that C 59N-C 60 intermolecular interactions are weak.

  9. Anti-Influenza Activity of C60 Fullerene Derivatives

    PubMed Central

    Shoji, Masaki; Takahashi, Etsuhisa; Hatakeyama, Dai; Iwai, Yuma; Morita, Yuka; Shirayama, Riku; Echigo, Noriko; Kido, Hiroshi; Nakamura, Shigeo; Mashino, Tadahiko; Okutani, Takeshi; Kuzuhara, Takashi

    2013-01-01

    The H1N1 influenza A virus, which originated in swine, caused a global pandemic in 2009, and the highly pathogenic H5N1 avian influenza virus has also caused epidemics in Southeast Asia in recent years. Thus, the threat from influenza A remains a serious global health issue, and novel drugs that target these viruses are highly desirable. Influenza A RNA polymerase consists of the PA, PB1, and PB2 subunits, and the N-terminal domain of the PA subunit demonstrates endonuclease activity. Fullerene (C60) is a unique carbon molecule that forms a sphere. To identify potential new anti-influenza compounds, we screened 12 fullerene derivatives using an in vitro PA endonuclease inhibition assay. We identified 8 fullerene derivatives that inhibited the endonuclease activity of the PA N-terminal domain or full-length PA protein in vitro. We also performed in silico docking simulation analysis of the C60 fullerene and PA endonuclease, which suggested that fullerenes can bind to the active pocket of PA endonuclease. In a cell culture system, we found that several fullerene derivatives inhibit influenza A viral infection and the expression of influenza A nucleoprotein and nonstructural protein 1. These results indicate that fullerene derivatives are possible candidates for the development of novel anti-influenza drugs. PMID:23785493

  10. Anti-influenza activity of c60 fullerene derivatives.

    PubMed

    Shoji, Masaki; Takahashi, Etsuhisa; Hatakeyama, Dai; Iwai, Yuma; Morita, Yuka; Shirayama, Riku; Echigo, Noriko; Kido, Hiroshi; Nakamura, Shigeo; Mashino, Tadahiko; Okutani, Takeshi; Kuzuhara, Takashi

    2013-01-01

    The H1N1 influenza A virus, which originated in swine, caused a global pandemic in 2009, and the highly pathogenic H5N1 avian influenza virus has also caused epidemics in Southeast Asia in recent years. Thus, the threat from influenza A remains a serious global health issue, and novel drugs that target these viruses are highly desirable. Influenza A RNA polymerase consists of the PA, PB1, and PB2 subunits, and the N-terminal domain of the PA subunit demonstrates endonuclease activity. Fullerene (C60) is a unique carbon molecule that forms a sphere. To identify potential new anti-influenza compounds, we screened 12 fullerene derivatives using an in vitro PA endonuclease inhibition assay. We identified 8 fullerene derivatives that inhibited the endonuclease activity of the PA N-terminal domain or full-length PA protein in vitro. We also performed in silico docking simulation analysis of the C60 fullerene and PA endonuclease, which suggested that fullerenes can bind to the active pocket of PA endonuclease. In a cell culture system, we found that several fullerene derivatives inhibit influenza A viral infection and the expression of influenza A nucleoprotein and nonstructural protein 1. These results indicate that fullerene derivatives are possible candidates for the development of novel anti-influenza drugs.

  11. Thermoelectricity in vertical graphene-C60-graphene architectures.

    PubMed

    Wu, Qingqing; Sadeghi, Hatef; García-Suárez, Víctor M; Ferrer, Jaime; Lambert, Colin J

    2017-09-15

    Recent studies of single-molecule thermoelectricity have identified families of high-performance molecules. However, in order to translate this discovery into practical thin-film energy-harvesting devices, there is a need for an understanding of the fundamental issues arising when such junctions are placed in parallel. This is relevant because controlled scalability might be used to boost electrical and thermoelectric performance over the current single-junction paradigm. As a first step in this direction, we investigate here the properties of two C60 molecules placed in parallel and sandwiched between top and bottom graphene electrodes. In contrast with classical conductors, we find that increasing the number of parallel junctions from one to two can cause the electrical conductance to increase by more than a factor of 2. Furthermore, we show that the Seebeck coefficient is sensitive to the number of parallel molecules sandwiched between the electrodes, whereas classically it should be unchanged. This non-classical behaviour of the electrical conductance and Seebeck coefficient are due to inter-junction quantum interference, mediated by the electrodes, which leads to an enhanced response in these vertical molecular devices.

  12. Study of IR laser photoacoustic spectra of organic molecules adsorbed on metal surface

    NASA Astrophysics Data System (ADS)

    Lu, Huizong; Chen, Kaitai; Wang, Zhaoyong

    1987-06-01

    Using a branch-tuning CW CO2 laser in the range of 0.2 to 10.8 microns, the IR photoacoustic spectra of organic molecules absorbed on a silver surface were studied. The absorbed molecular spectra of four layers of arachidic acid and cellulose diacetate with different surface densities was studied. No peak shift was found in a comparison between IR photoacoustic spectra of solid arachidic acid near 944/cm and the corresponding IR Fourier spectra of solid archidic acid. The IR photoacoustic spectra of cellulose diacetate with sigma sub 1 = 14,000/sq cm and sigma sub 1 = 5.5 x 10 to the 15th/sq cm respectively was compared with the corresponding transmission spectra of solid cellulose diacetate. It was found that the peak of the former near 1054/cm had a red shift of about 5/cm while the peak of the latter had no obvious shift within the range of accuracy of the experiment.

  13. Raman rotational spectra of endohedral C60 fullerene complexes

    NASA Astrophysics Data System (ADS)

    Hernández-Rojas, J.; Bretón, J.; Gomez Llorente, J. M.

    1996-09-01

    Low-temperature (T=50 K) Raman rotational spectra are calculated for the endohedral complexes Li+@C60, Na+@C60, CO@C60, LiF@C60, and LiH@C60. The systems Na+@C60 and CO@C60 produce very similar spectra dominated by pure rotational bands. The other systems present more complex and dissimilar spectra which suggest librational motions and hindered rotations. An assignment of these spectra is provided by analyzing the structure of the low energy rotational eigenvalues and eigenfunctions. Rotational energy quasiband and quasiresonance-band structures are found to be the origin of the features observed in the more complex spectra. Out of these analyses, a classification of the low-temperature rotational spectra of endohedral C60 complexes in two basic classes emerges.

  14. Multiscale dynamics of C60 from attosecond to statistical physics

    NASA Astrophysics Data System (ADS)

    Lépine, F.

    2015-06-01

    C60 is a fascinating object that has become remarkably useful for experimentalists and theoreticians to study photo-induced processes in large many-particle systems. In this review article, we discuss how the knowledge accumulated over the past 30 years on this molecule provides a large panel of mechanisms that occur from the intrinsic time scale of electronic motion that is attosecond, to long ‘macroscopic’ time scale (second). This illustrates the multiscale aspect of dynamics in photo-excited systems, which connects coherent quantum processes to classical and statistical mechanisms. This also shines light onto future experiments and theoretical work required to complete the global picture of light-induced mechanisms in fullerenes.

  15. 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

  16. 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...

  17. 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 ...

  18. 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...

  19. 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...

  20. 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...

  1. Photon-exposure-dependent photon-stimulated desorption for obtaining photolysis cross section of molecules adsorbed on surface by monochromatic soft x-ray photons.

    PubMed

    Chou, L-C; Jang, C-Y; Wu, Y-H; Tsai, W-C; Wang, S-K; Chen, J; Chang, S-C; Liu, C-C; Shai, Y; Wen, C-R

    2008-12-07

    Photon-exposure-dependent positive- and negative-ion photon-stimulated desorption (PSD) was proposed to study the photoreactions and obtain the photolysis cross sections of molecules adsorbed on a single-crystal surface by monochromatic soft x-ray photons with energy near the core level of adsorbate. The changes in the F(+) and F(-) PSD ion yields were measured from CF(3)Cl molecules adsorbed on Si(111)-7x7 at 30 K (CF(3)Cl dose=0.3x10(15) molecules/cm(2), approximately 0.75 monolayer) during irradiation of monochromatic soft x-ray photons near the F(1s) edge. The PSD ion yield data show the following characteristics: (a) The dissociation of adsorbed CF(3)Cl molecules is due to a combination of direct photodissociation via excitation of F(1s) core level and substrate-mediated dissociation [dissociative attachment and dipolar dissociation induced by the photoelectrons emitting from the silicon substrate]. (b) the F(+) ion desorption is associated with the bond breaking of the surface CF(3)Cl, CF(2)Cl, CFCl, and SiF species. (c) the F(-) yield is mainly due to DA and DD of the adsorbed CF(3)Cl molecules. (d) The surface SiF is formed by reaction of the surface Si atom with the neutral fluorine atom, F(+), or F(-) ion produced by scission of C-F bond of CF(3)Cl, CF(2)Cl, or CFCl species. A kinetic model was proposed for the explanation of the photolysis of this submonolayer CF(3)Cl-covered surface. Based on this model and the variation rates of the F(+)F(-) signals during fixed-energy monochromatic photon bombardment at 690.2 and 692.6 eV [near the F(1s) edge], the photolysis cross section was deduced as a function of energy.

  2. Photon-exposure-dependent photon-stimulated desorption for obtaining photolysis cross section of molecules adsorbed on surface by monochromatic soft x-ray photons

    NASA Astrophysics Data System (ADS)

    Chou, L.-C.; Jang, C.-Y.; Wu, Y.-H.; Tsai, W.-C.; Wang, S.-K.; Chen, J.; Chang, S.-C.; Liu, C.-C.; Shai, Y.; Wen, C.-R.

    2008-12-01

    Photon-exposure-dependent positive- and negative-ion photon-stimulated desorption (PSD) was proposed to study the photoreactions and obtain the photolysis cross sections of molecules adsorbed on a single-crystal surface by monochromatic soft x-ray photons with energy near the core level of adsorbate. The changes in the F+ and F- PSD ion yields were measured from CF3Cl molecules adsorbed on Si(111)-7×7 at 30K (CF3Cl dose=0.3×1015molecules/cm2, ˜0.75 monolayer) during irradiation of monochromatic soft x-ray photons near the F(1s ) edge. The PSD ion yield data show the following characteristics: (a) The dissociation of adsorbed CF3Cl molecules is due to a combination of direct photodissociation via excitation of F(1s ) core level and substrate-mediated dissociation [dissociative attachment and dipolar dissociation induced by the photoelectrons emitting from the silicon substrate]. (b) the F+ ion desorption is associated with the bond breaking of the surface CF3Cl, CF2Cl, CFCl, and SiF species. (c) the F - yield is mainly due to DA and DD of the adsorbed CF3Cl molecules. (d) The surface SiF is formed by reaction of the surface Si atom with the neutral fluorine atom, F +, or F- ion produced by scission of C-F bond of CF3Cl, CF2Cl, or CFCl species. A kinetic model was proposed for the explanation of the photolysis of this submonolayer CF3Cl-covered surface. Based on this model and the variation rates of the F +/F- signals during fixed-energy monochromatic photon bombardment at 690.2 and 692.6eV [near the F(1s ) edge], the photolysis cross section was deduced as a function of energy.

  3. Effect of side by side interactions on the thermodynamic properties of adsorbed CO molecules on the Ni(111) surface: a cluster model study

    NASA Astrophysics Data System (ADS)

    Shamkhali, Amir N.; Parsafar, Gholamabbas

    2010-05-01

    The effect of electrostatic interactions on vibrational frequencies and thermodynamic properties of CO adsorbate on the Ni(111) surface is calculated by taking the first and second nearest-neighbour interactions into account. In order to obtain reasonable results, the cluster model of various surface adsorption sites with CO adsorbate is partially optimized, using Density Functional Theory and also the MP2 method for the hcp site. Comparison between DFT and MP2 results shows that DFT results are more reliable for this system. The stretching and bending frequencies of CO adsorbate are calculated using both Partial Hessian Analysis and Cluster-Adsorbate Coupling methods. Stretching and bending frequencies are both shifted by the side by side interactions. The coupling of surface phonons and adsorbate vibrations reduces the side effects. The largest side effects on the vibrational internal energy, isochoric heat capacity, entropy and total Helmholtz free energy of adsorbed CO molecule calculated using the CAC method are found for 0.5 ML coverage. The results of the CAC method are better, but the PHA method can be used as a simple upper bound estimation. The adsorptive phase acts as an intelligent material in such a way that it changes its configuration in order to reduce the side effects.

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

    SciTech Connect

    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.

  5. Molecular dynamics simulations on the interactions of low molecular weight natural organic acids with C60.

    PubMed

    Sun, Qian; Xie, Hong-Bin; Chen, Jingwen; Li, Xuehua; Wang, Zhuang; Sheng, Lianxi

    2013-07-01

    As an important part of dissolved organic matter (DOM), low molecular weight organic acids (LOAs) may play a key role in the process for DOM stabilizing carbon nanomaterials (e.g. C60) suspensions in aquatic environment. In addition, both LOAs and C60 have been detected in the troposphere and therefore have a chance to interact with each other in the gaseous phase. However, the mechanism for LOAs-C60 interactions and their environmental implications need further investigations. In this study, molecular dynamics (MD) simulation was employed to investigate the interactions between both neutral and ionic LOAs with C60 in vacuum and water. The results showed that the adsorptions of all LOAs on C60 in energy are favorable, and the aromatic acids have stronger interactions with C60 than the aliphatic acids in vacuum and water. The interaction energies (Eint) of the LOA anions with C60 were weaker than those of their corresponding neutral LOA molecules. The models were also developed to predict and interpret Eint based on the results from MD simulations. Dispersion, induction and hydrophobic interactions were found to be the dominating factor in Eint. These findings indicate that cost-efficient MD simulation can be employed as an important tool to predict the adsorption behavior of LOAs on carbon nanomaterials.

  6. Between Crystal and Glass: Thermal Transport in C60 Molecular Crystals

    NASA Astrophysics Data System (ADS)

    Lu, Simon; Kumar, Sushant; McGaughey, Alan

    Molecular crystals of the fullerene C60 and its derivatives [e.g., phenyl-C61-butyric acid methyl ester (PCBM)] are candidate materials for use in photovoltaics and thermoelectrics. In thermoelectrics, their usefulness is due in part to their exceptionally low thermal conductivities (0.4 W/m-K for C60 and 0.05 W/m-K for PCBM) at room temperature. Little is known regarding the microscopic physics underlying these low thermal conductivities. An important question is whether thermal transport in the C60 molecular crystal is (i) crystal-like, where energy is transported as collective vibrations of the centers of mass of the molecules, or (ii) amorphous-like, where energy diffuses from molecule to molecule. We use molecular dynamics (MD) simulations and the Green-Kubo method to probe this question by predicting the relative contributions of crystal-like and amorphous-like transport to the thermal conductivity of the C60 molecular crystal. To isolate crystal-like transport, we perform simulations on C60 crystals where molecular rotations and intra-molecular vibrations are prohibited. To isolate amorphous-like transport, we fix the centers of mass of the molecules. We compare the MD results to predictions from a fully diffusive network resistance model. This work is supported by the National Science Foundation (Grant DMR-1507325).

  7. 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...

  8. 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...

  9. Confinement and cavity effects in time-domain photoionization and recombination of Kr@C60

    NASA Astrophysics Data System (ADS)

    Magrakvelidze, Maia; Dixit, Gopal; Madjet, Mohamed; Chakraborty, Himadri

    2014-05-01

    Photoionization (PI) and radiative recombination (RR) of the endofullerene molecule, Kr@C60, are studied in a framework of time-dependent local density approximation (TDLDA) augmented by the Leeuwen and Baerends exchange-correlation functional. Phases of the dipole matrix elements corresponding to transitions to (PI) and from (RR) the continuum, involving atomic-type, fullerene-type and atom-fullerene hybrid levels of the molecule, are considered. Associated Wigner-Smith time-delays are extracted. Effects of the confinement on the phase and time-delay at Kr Cooper minima, and that of the C60 cavity at C60 cross section minima have been examined. Further, intercoulombic decay (ICD) and hybrid Auger-ICD resonances, direct results of the confinement, are found to considerably enrich the time-domain response of the molecule. This work was supported by the National Science Foundation.

  10. Method for the calculation of the vibrational frequency shift of physisorbed molecules. Application to H2 adsorbed in NaA zeolite

    NASA Astrophysics Data System (ADS)

    Larin, A. V.; Cohen De Lara, E.

    1994-11-01

    The vibrational frequency shift of physisorbed diatomic molecules is related to the interaction with the adsorbent expressed in terms of the internuclear distance ρ. It is calculated by the Schrödinger equation, the perturbation theory, and a simplified method. We show that it is sufficient to calculate the interaction potential for the values of ρ in the ground and first vibrational states in order to get a precision of 10% on the frequency shift. The comparison between the theoretical and experimental frequency shift of H2 adsorbed in NaA zeolite is used to adjust the interaction potential, especially in terms of the ionicity of the crystal.

  11. Search for Hydrogenated C60 (Fulleranes) in Circumstellar Envelopes

    NASA Astrophysics Data System (ADS)

    Zhang, Yong; Sadjadi, SeyedAbdolreza; Hsia, Chih-Hao; Kwok, Sun

    2017-08-01

    The recent detection of fullerene (C60) in space and the positive assignment of five diffuse interstellar bands to {{{C}}}60+ reinforce the notion that fullerene-related compounds can be efficiently formed in circumstellar envelopes and be present in significant quantities in the interstellar medium. Experimental studies have shown that C60 can be readily hydrogenated, raising the possibility that hydrogenated fullerenes (or fulleranes, C60H m , m = 1-60) may be abundant in space. In this paper, we present theoretical studies of the vibrational modes of isomers of C60H m . Our results show that the four mid-infrared bands from the C60 skeletal vibrations remain prominent in slightly hydrogenated C60, but their strengths diminish in different degrees with increasing hydrogenation. It is therefore possible that the observed infrared bands assigned to C60 could be due to a mixture of fullerenes and fulleranes. This provides a potential explanation for the observed scatter of the C60 band ratios. Our calculations suggest that a feature around 15 μm due to the breathing mode of heavily hydrogenated C60 may be detectable astronomically. A preliminary search for this feature in 35 C60 sources is reported.

  12. Synthesis and high pressure induced amorphization of C60 nanosheets

    NASA Astrophysics Data System (ADS)

    Wang, Lin; Liu, Bingbing; Liu, Dedi; Yao, Mingguang; Yu, Shidan; Hou, Yuanyuan; Zou, Bo; Cui, Tian; Zou, Guangtian; Sundqvist, Bertil; Luo, Zongju; Li, Hui; Li, Yanchun; Liu, Jing; Chen, Shijian; Wang, Guorui; Liu, Yichun

    2007-09-01

    C60 nanosheets with thicknesses in the nanometer range were synthesized by a simple method. Compared to bulk C60, the lattice of the nanosheets is expanded by about 0.4%. In situ Raman spectroscopy and energy-dispersive x-ray diffraction under high pressures have been employed to study the structure of the nanosheets. The studies indicate that the bulk modulus of the C60 nanosheets is significantly larger than that of bulk C60. The C60 cages in nanosheets can persist at pressures over 30GPa, 3GPa higher than for bulk C60. These results suggest that C60 crystals in even small size will be a potential candidate of superhard materials.

  13. Theoretical characterisation of irreversible and reversible hydrogen storage reactions on Ni-doped C60 fullerene

    NASA Astrophysics Data System (ADS)

    Shalabi, A. S.; El Mahdy, A. M.; Soliman, K. A.; Taha, H. O.

    2014-12-01

    An attempt has been made to characterise the irreversible and reversible hydrogen storage reactions on Ni-doped C60 fullerene by using the state of the art density functional theory calculations. The single Ni atom prefers to bind at the bridge site between two hexagonal rings of C60 fullerene, and can bind up to four hydrogen molecules with average adsorption energies of -0.85, -0.83, -0.58, and -0.31 eV per hydrogen molecule. No evidence for metal clustering in the ideal circumstances and the hydrogen storage capacity is expected to be as large as 8.9 wt%. While the desorption activation barriers of the complexes nH2NiC60 (n = 1, 2) are outside the desirable energy window recommended by the department of energy for practical applications (-0.2 to -0.6 eV), the desorption activation barriers of the complexes nH2NiC60 (n = 3, 4) are inside this window. The irreversible 2H2 + NiC60 and reversible 3H2 + NiC60 interactions are characterised in terms of several theoretical parameters such as: (1) densities of states and projected densities of states, (2) pairwise and non-pairwise additivity, (3) infrared, Raman, and proton magnetic resonance spectra, (4) electrophilicity, and (5) statistical thermodynamic stability.

  14. 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

  15. Rotational reorientation dynamics of C60 in various solvents. Picosecond transient grating experiments

    NASA Astrophysics Data System (ADS)

    Rubtsov, I. V.; Khudiakov, D. V.; Nadtochenko, V. A.; Lobach, A. S.; Moravskii, A. P.

    1994-11-01

    The picosecond transient grating technique has been used to study the rotational reorientation of C60 in various solvents: in toluene 7 +/- 1.5 ps, o-dichlorobenzene 10.3 +/- 1.5 ps, o-xylene 13 +/- 2 ps and in decalin 3.5 +/- 1.5 ps. The data obtained cannot be described by hydrodynamic Debye theory. Rough-sphere fluid theory predicts the correct values for C60 rotation in toluene, o-dichlorobenzene and in decalin. The deviations for o-xylene are probably connected with the specifics of the local solvent structure or with the stronger interaction of C60 with solvent molecules. The rotation of C60 in decalin is rapid and approaches the rotation in the gas phase determined by inertia.

  16. Attosecond study of confinement in photoionization of xenon caged in C60

    NASA Astrophysics Data System (ADS)

    Magrakvelidze, Maia; Dixit, Gopal; Madjet, Mohamed; Chakraborty, Himadri

    2015-05-01

    Effects of atom-fullerene orbital hybridization and C60 cavity on the attosecond time delay of the photoionization of Xe in the Xe@C60 endohedral molecule are investigated using time dependent local density approximation (TDLDA) augmented by the Leeuwen and Baerends exchange-correlation functional. TDLDA Wigner-Smith delay is found to modify via three distinct mechanisms: (i) Screening (or anti-screening) of the atomic valence emission due to the plasmonic motions of C60 charge cloud; (ii) dynamical interactions between Xe Cooper minima and C60 cavity minima; and (iii) confinement oscillations in the photoionization of inner 4d shell of Xe from the resonant formation of standing waves inside the cavity. The effects may be experimentally accessible by the so called RABITT metrology. This work was supported by the U.S. National Science Foundation.

  17. 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.

  18. Orientational order in the stable buckminster fullerene solvate C60·2CBr2H2

    NASA Astrophysics Data System (ADS)

    Ye, J.; Barrio, M.; Negrier, Ph.; Qureshi, N.; Rietveld, I. B.; Céolin, R.; Tamarit, J. Ll.

    2017-04-01

    Crystals of the solvate C60·2CBr2H2 (monoclinic C2/ m), which is stable in air, were grown by slow evaporation of solutions of C60 in CBr2H2 at room temperature. The high enthalpy change for the complete desolvation process, 54.9 kJ mol-1 of solvent, as well as the relatively large negative excess volume of -49.6 Å3 indicate the presence of strong intermolecular interactions between C60 and CBr2H2. The strong intermolecular interactions are consistent with an overall orientational order for the C60 and the CBr2H2 molecules in the solvate as found by the Rietveld refinement of its crystal structure.

  19. Production of Self-Assembled Fullerene (C60) Nanocrystals at Liquid-Liquid Interface.

    PubMed

    Shrestha, Rekha Goswami; Shrestha, Lok Kumar; Abe, Masahiko; Ariga, Katsuhiko

    2015-03-01

    Here we present self-assembled nanostructure of functional molecule fullerene (C60) at liquid-liquid interface. The nanostructured nanocrystals were grown at liquid-liquid interface of isopropyl alcohol (IPA) and C60 solution in butylbenzene under ambient condition of temperature and pressure, and characterized by Raman scattering, power X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The crystal formation mechanism is driven by supersaturation related to the low solubility of C60 in IPA. A slow diffusion of IPA towards the C60 solution causes unsaturation of C60 at the liquid-liquid interface and consequently small clusters of C60 is formed at the interface, which acts as the nucleation site. Further diffusion of IPA supplies the C60 molecules from bulk to the interface promoting the crystal growth. Based on SEM and TEM observation, the average size of the individual hexagonal bipyramid nanocrystal is found to be ca. 1.4 µm and the average size of their assembly is found to be approximately 2 µm. XRD measurements have shown that these materials are crystalline with mixed face-centered cubic (cell dimension: a = 1.352 nm, and V = 2.475 nm3) and hexagonal (cell dimension: a = 1.452 nm, c = 1.207 nm, c/a = 0.831, and V = 2.475 nm3) structures. Raman scattering measurements showed two Ag and six Hg vibration bands, which are similar to those obtained in the pristine C60.

  20. Temperature dependence of the electronic properties of K3C60 and K4C60 single-phase films investigated by means of electron spectroscopies

    NASA Astrophysics Data System (ADS)

    Goldoni, A.; Sangaletti, L.; Friedmann, S. L.; Shen, Z.-X.; Peloi, M.; Parmigiani, F.; Comelli, G.; Paolucci, G.

    2000-11-01

    The normal state temperature dependence of a metallic K3C60 phase pure film has been investigated by means of core levels and valence band photoemission, carbon K edge x-ray absorption, and electron energy loss spectroscopies and compared with that of a Mott-Hubbard insulating K4C60 film. The anomalous temperature behavior of K3C60, in the range 30 K-600 K, can be consistently interpreted considering the presence of orientational disorder of the C60 molecules together with the inhomogeneity of the conduction electron distribution at the molecular level. In particular, the changes observed in the photoemission spectra near the Fermi level, are consistent with the behavior predicted for strongly correlated metallic systems in presence of disorder. Also in the case of K4C60 we observe anomalies in the temperature dependence of core levels photoemission data. These anomalies can be explained with the freezing of the molecular motions at low temperature and point to large thermal fluctuations of the alkali atoms around their equilibrium position at high temperature.

  1. Stability of (C60)2 and epoxide dimers, (C60)2ON, and their anions.

    PubMed

    Owens, Frank J

    2005-06-01

    The PM3, AM1, and MINDO3 semiemperical methods are used to calculate the the energy difference between C60ON and C60ON- and the bond dissociation energy necessary to cleave neutral and negatively charged (C60)2 dimers and epoxide dimers, (C60)2ON, to their respective monomers C60, and C60ON/2. The results show that the anions of the dimers are significantly more stable than neutral dimers. This result may explain the higher thermal stability of the observed ferromagnetic phase in photolyzed C60. which has been attributed to epoxide dimers and oligomers. It also provides an explanation for the origin of unpaired electron spin necessary for ferromagnetism.

  2. Laser desorption of NO from a thick C 60 film

    NASA Astrophysics Data System (ADS)

    Hoger, T.; Marzok, C.; Jongma, R. T.; Zacharias, H.

    2006-09-01

    The desorption of NO molecules from a thick C 60 film is reported. A thermal desorption spectrum indicates two adsorption sites with binding energies of Eb = 0.30 eV and 0.55 eV. For laser desorption the fullerene surface is exposed to NO and excited by 7 ns UV laser pulses. Desorbing NO molecules are recorded state selectively as well as time resolved. The time-of-flight measurement indicates three different desorption pathways. A fast channel shows rovibronic temperatures of Trot( v″ = 0) = 370 K, Trot( v″ = 1) = 390 K and Tvib = 610 K as well as strong rotational-translational coupling. The desorption yield for the fast channel increases linearly with pulse energy with a desorption cross section of σ = (5.1 ± 0.9) × 10 -17 cm 2. Dominating the signal for small J″ values is a slow channel with low rotational and translational temperatures of about 110 K. We assign this peak to a laser-induced thermal desorption. For large pump-probe delays the data deviate from the Maxwellian flux distribution and a third channel appears with extremely late arrival times.

  3. In situ STM imaging of bis-3-sodiumsulfopropyl-disulfide molecules adsorbed on copper film electrodeposited on Pt(111) single crystal electrode.

    PubMed

    Tu, HsinLing; Yen, PoYu; Chen, Sihzih; Yau, ShuehLin; Dow, Wei-Ping; Lee, Yuh-Lang

    2011-06-07

    The adsorption of bis-3-sodiumsulfopropyldi-sulfide (SPS) on metal electrodes in chloride-containing media has been intensively studied to unveil its accelerating effect on Cu electrodeposition. Molecular resolution scanning tunneling microscopy (STM) imaging technique was used in this study to explore the adsorption and decomposition of SPS molecules concurring with the electrodeposition of copper on an ordered Pt(111) electrode in 0.1 M HClO(4) + 1 mM Cu(ClO(4))(2) + 1 mM KCl. Depending on the potential of Pt(111), SPS molecules could react, adsorb, and decompose at chloride-capped Cu films. A submonolayer of Cu adatoms classified as the underpotential deposition (UPD) layer at 0.4 V (vs Ag/AgCl) was completely displaced by SPS molecules, possibly occurring via RSSR (SPS) + Cl-Cu-Pt → RS(-)-Pt(+) + RS(-) (MPS) + Cu(2+) + Cl(-), where MPS is 3-mercaptopropanesulfonate. By contrast, at 0.2 V, where a full monolayer of Cu was presumed to be deposited, SPS molecules were adsorbed in local (4 × 4) structures at the lower ends of step ledges. Bulk Cu deposition driven by a small overpotential (η < 50 mV) proceeded slowly to yield an atomically smooth Cu deposit at the very beginning (<5 layers). On a bilayer Cu deposit, the chloride adlayer was still adsorbed to afford SPS admolecules arranged in a unique 1D striped phase. SPS molecules could decompose into MPS upon further Cu deposition, as a (2 × 2)-MPS structure was observed with prolonged in situ STM imaging. It was possible to visualize either SPS admolecules in the upper plane or chloride adlayer sitting underneath upon switching the imaging conditions. Overall, this study established a MPS molecular film adsorbed to the chloride adlayer sitting atop the Cu deposit.

  4. Observation of Ground- and Excited-State Charge Transfer at the C60/Graphene Interface.

    PubMed

    Jnawali, Giriraj; Rao, Yi; Beck, Jonathan H; Petrone, Nicholas; Kymissis, Ioannis; Hone, James; Heinz, Tony F

    2015-07-28

    We examine charge transfer interactions in the hybrid system of a film of C60 molecules deposited on single-layer graphene using Raman spectroscopy and Terahertz (THz) time-domain spectroscopy. In the absence of photoexcitation, we find that the C60 molecules in the deposited film act as electron acceptors for graphene, yielding increased hole doping in the graphene layer. Hole doping of the graphene film by a uniform C60 film at a level of 5.6 × 10(12)/cm(2) or 0.04 holes per interfacial C60 molecule was determined by the use of both Raman and THz spectroscopy. We also investigate transient charge transfer occurring upon photoexcitation by femtosecond laser pulses with a photon energy of 3.1 eV. The C60/graphene hybrid exhibits a short-lived (ps) decrease in THz conductivity, followed by a long-lived increase in conductivity. The initial negative photoconductivity transient, which decays within 2 ps, reflects the intrinsic photoresponse of graphene. The longer-lived positive conductivity transient, with a lifetime on the order of 100 ps, is attributed to photoinduced hole doping of graphene by interfacial charge transfer. We discuss possible microscopic pathways for hot carrier processes in the hybrid system.

  5. 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

  6. Electron Spin Density Distribution in the Polymer Phase of CsC60: Assignment of the NMR Spectrum

    NASA Astrophysics Data System (ADS)

    de Swiet, T. M.; Yarger, J. L.; Wagberg, T.; Hone, J.; Gross, B. J.; Tomaselli, M.; Titman, J. J.; Zettl, A.; Mehring, M.

    2000-01-01

    We present high resolution 133Cs-13C double resonance NMR data and 13C-13C NMR correlation spectra of 13C enriched samples of the polymeric phase of CsC60. These data lead to a partial assignment of the lines in the 13C NMR spectrum of CsC60 to the carbon positions on the C60 molecule. A plausible completion of the assignment can be made on the basis of an ab initio calculation. The data support the view that the conduction electron density is concentrated at the C60 ``equator,'' away from the interfullerene bonds.

  7. Enhancing the colloidal stability of detonation synthesized diamond particles in aqueous solutions by adsorbing organic mono-, bi- and tridentate molecules.

    PubMed

    Wang, Tao; Handschuh-Wang, Stephan; Qin, Panpan; Yang, Yang; Zhou, Xuechang; Tang, Yongbing

    2017-08-01

    Colloidal stability of nanoparticles with particle sizes smaller than 100nm is a critical issue for various research areas, including material science, electronics and biomedicine. We propose a facile, fast and cost-efficient method to increase the colloidal stability by simply adding organic molecules as ligands, which adsorb to the nanoparticle surface subsequently. Citric acid, oxalic acid, glutamic acid and propylamine were found to stabilize the nanodiamond (ND) particles with a mean diameter of approx. 30-100nm. The charge of the particles could be controlled by the pH of the dispersions and by stabilizing with carboxylic acids or amino acids mentioned above. ND particles stabilized with citric acid and oxalic acid at a pH higher than 2.5 were negatively charged, while ND dispersions stabilized with glutamic acid were charged positively below a pH of 3.2. Furthermore, the stability of the dispersion was found to be dependent on the concentration of the stabilizing agent and the pH of the dispersion. Finally, we proposed the stabilizing mechanism of ND particles with propylamine. Glutamic acid and propylamine stabilized ND dispersions can be utilized for high seeding densities on negatively charged surfaces due to the amino-groups, which can be helpful for adsorption processes in electronics and material science. Due to the high biocompatibility, non-cytotoxicity and chemical inertness of ND particles, carboxylic acids and amino acids stabilized ND particles are envisaged to be useful in the biomedical field, i.e. bio-labels, drug delivery vehicles, and effective enterosorbent. Copyright © 2017 Elsevier Inc. All rights reserved.

  8. Interaction of porphine and its metal complexes with C60 fullerene: a DFT study.

    PubMed

    Basiuk, Vladimir A

    2005-04-28

    We performed DFT calculations (BLYP general-gradient approximation in conjunction with a double numerical basis set) for the interaction of free porphine ligand and a number of its metal complexes with C60 molecule to analyze how the nature of a central metal ion influences the geometry and electronic characteristics (electrostatic potential and spin density distribution and highest-occupied molecular orbital (HOMO) and lowest-unoccupied molecular orbital (LUMO) structure). We found that the presence of a central metal ion is crucial for a strong interaction. The energy of interaction between H2P and C60 is -0.3 kcal mol(-1) only, whereas the formation energies for the metal complexes vary from -27.3 kcal mol(-1) for MnClP.C60 to -45.8 kcal mol(-1) for MnP.C60. As a rule, the formation energy correlates with the separations between porphinate and fullerene molecules; the Mn and Fe complexes exhibit the closest approach of ca. 2.2 A between the metal ion and carbon atoms of C60. In most porphine-C60 complexes studied, the two closest contacts of central metal ion or H are those with carbon atoms of the (6,6) bond; VOP.C60 is the only exception, where the closest V...C contacts involve the (5,6) bond. The macrocycle geometry changes, and the magnitude of the effect depends on the central atom, being especially dramatic for Mn, MnCl, and Fe complexes. The shape of LUMOs in most complexes with C60 is not affected notably as compared to the LUMO of the isolated C60 molecule. In the case of Fe, the HOMO extends from the central atom to two opposite pyrrol rings. At the same time, the HOMO-LUMO gap energy decreases drastically in most cases, by ca. 20-30 kcal mol(-1). For electrostatic potential distribution, we systematically observed that the negative lobe contacting C60 shrinks, whereas the opposite one becomes notably bigger. In the case of paramagnetic complexes of VO, Mn, FeCl, Co, and Cu, spin density distribution was analyzed as well.

  9. Controlling the Electronic and Structural Coupling of C60 Nano Films on Fe(001) through Oxygen Adsorption at the Interface.

    PubMed

    Picone, Andrea; Giannotti, Dario; Riva, Michele; Calloni, Alberto; Bussetti, Gianlorenzo; Berti, Giulia; Duò, Lamberto; Ciccacci, Franco; Finazzi, Marco; Brambilla, Alberto

    2016-10-05

    C60 molecules coupled to metals form hybrid systems exploited in a broad range of emerging fields, such as nanoelectronics, spintronics, and photovoltaic solar cells. The electronic coupling at the C60/metal interface plays a crucial role in determining the charge and spin transport in C60-based devices; therefore, a detailed understanding of the interface electronic structure is a prerequisite to engineering the device functionalities. Here, we compare the electronic and structural properties of C60 monolayers interfaced with Fe(001) and oxygen-passivated Fe(001)-p(1 × 1)O substrates. By combining scanning tunneling microscopy and spectroscopy, Auger electron spectroscopy, photoemission and inverse photoemission spectroscopies, we are able to elucidate the striking effect of oxygen on the interaction between Fe(001) and C60. Upon C60 deposition on the oxygen-passivated surface, the oxygen layer remains buried at the C60/Fe(001)-p(1 × 1)O interface, efficiently decoupling the fullerene film from the metallic substrate. Tunneling and photoemission spectroscopies reveal the presence of well-defined molecular resonances for the C60/Fe(001)-p(1 × 1)O system, with a large HOMO-LUMO gap of about 3.4 eV. On the other hand, for the C60/Fe(001) interface, a strong hybridization between the substrate states and the C60 orbitals occurs, resulting in broader molecular resonances.

  10. 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.

  11. Electronic Structure Investigation of Doping C60 with Metal Oxide

    NASA Astrophysics Data System (ADS)

    Wang, Chenggong; Gao, Yongli

    2014-03-01

    Fullerene (C60) has been used extensively as an acceptor material in organic photovoltaic (OPV) cells. Other applications including n-channel organic thin film transistors (OTFT) and C60 based organic superconductors have been reported more than a decade ago. We have investigated p-doping of C60 with molybdenum oxide (MoOx) with ultra-violet photoemission spectroscopy (UPS), inverse photoemission spectroscopy (IPES) and atomic force microscopy (AFM). Both surface doping and bulk doping by MoOx are studied. It was found that the thermally evaporated MoOx inter-layer substantially increased the surface workfunction. This increased surface workfunction strongly attract electrons towards the MoOx layer at the C60/MoOx interface, resulting in strong inversion of C60. Energy levels of C60 relax gradually as the thickness of C60 increases. An exceptionally long (greater than 400 Angstrom) band bending is observed during this relaxation in C60. Such a long band bending has not been observed for other organic/MoOx interface. For the bulk doping, MoOx doping ratios from 1% to over 100% were investigated. The saturation occurs at approximately 20 %, when the highest occupied molecular level (HOMO) of C60 starts to be pinned at the Fermi level. These studies demonstrate effective ways to manipulate the electronic structures of the fullerene. This work is supported by the National Science Foundation Grant No. DMR-1303742.

  12. Ordered phases of ethylene adsorbed on charged fullerenes and their aggregates☆

    PubMed Central

    Zöttl, Samuel; Kaiser, Alexander; Daxner, Matthias; Goulart, Marcelo; Mauracher, Andreas; Probst, Michael; Hagelberg, Frank; Denifl, Stephan; Scheier, Paul; Echt, Olof

    2014-01-01

    In spite of extensive investigations of ethylene adsorbed on graphite, bundles of nanotubes, and crystals of fullerenes, little is known about the existence of commensurate phases; they have escaped detection in almost all previous work. Here we present a combined experimental and theoretical study of ethylene adsorbed on free C60 and its aggregates. The ion yield of (C60)m(C2H4)n+ measured by mass spectrometry reveals a propensity to form a structurally ordered phase on monomers, dimers and trimers of C60 in which all sterically accessible hollow sites over carbon rings are occupied. Presumably the enhancement of the corrugation by the curvature of the fullerene surface favors this phase which is akin to a hypothetical 1 × 1 phase on graphite. Experimental data also reveal the number of molecules in groove sites of the C60 dimer through tetramer. The identity of the sites, adsorption energies and orientations of the adsorbed molecules are determined by molecular dynamics calculations based on quantum chemical potentials, as well as density functional theory. The decrease in orientational order with increasing temperature is also explored in the simulations whereas in the experiment it is impossible to vary the temperature. PMID:25843960

  13. Fullerene-C60 and crown ether doped on C60 sensors for high sensitive detection of alkali and alkaline earth cations

    NASA Astrophysics Data System (ADS)

    Zaghmarzi, Fatemeh Alipour; Zahedi, Mansour; Mola, Adeleh; Abedini, Saboora; Arshadi, Sattar; Ahmadzadeh, Saeed; Etminan, Nazanin; Younesi, Omran; Rahmanifar, Elham; Yoosefian, Mehdi

    2017-03-01

    Fullerenes are effective acceptor components with high electron affinity for charge transfer. The significant influences of chemical adsorption of the cations on the electrical sensitivity of pristine C60 and 15-(C2H4O)5/C60 nanocages could be the basis of new generation of electronic sensor design. The density functional theory calculation for alkali and alkaline earth cations detection by pristine C60 and 15-(C2H4O)5/C60 nanocages are considered at B3LYP level of theory with 6-31 G(d) basis set. The quantum theory of atoms in molecules analysis have been performed to understand the nature of intermolecular interactions between the cations and nanocages. Also, the natural bond orbital analysis have been performed to assess the intermolecular interactions in detail. Furthermore, the frontier molecular orbital, energy gap, work function, electronegativity, number of transferred electron (∆N), dipole moment as well as the related chemical hardness and softness are investigated and calculated in this study. The results show that the adsorption of cations (M=Na+, K+, Mg2+ and Ca2+) are exothermic and the binding energy in pristine C60 nanocage and 15-(C2H4O)5/C60 increases with respect to the cations charge. The results also denote a decrease in the energy gap and an increase in the electrical conductivity upon the adsorption process. In order to validate the obtained results, the density of state calculations are employed and presented in the end as well.

  14. Electronic structure and properties of highly ordered C60 nano arrays on Au (111): STM & DFT study

    NASA Astrophysics Data System (ADS)

    Win, Zaw-Myo; HUANG, Chao; ZHANG, Rui-Qin

    2017-06-01

    Template assisted assembly of molecular nano arrays is one of the key steps towards molecular electronics and fullerene is one of the potential structural building blocks in fabrication of identical molecular nano arrays for miniature devices such as photovoltaic devices and single-molecule transistors. In this report, the reconstructed Au (111) with defect areas (steps) has been used as a template to assemble the highly ordered C60 nano array at low coverage studied with scanning tunnelling microscopy (STM) in conjunction with density functional theory (DFT). The interaction between the substrate and C60 nano arrays is strong enough to change the geometrical shape of C60. As a result of strong interaction, the C60 molecule appears to be deformed into ellipsoidal shape which causes the reduction of C60 nano arrays on step sites of Au (111).

  15. Gold Cluster Formation on C60 Surfaces: Au-Cluster Beads and Self-Organized Structures

    NASA Astrophysics Data System (ADS)

    Reinke, Petra; Liu, Hui

    2007-03-01

    Petra Reinke, Hui Liu, Department of Materials Science and Engineering, University of Virginia The investigation of C60-Au interaction is central to the advancement of solar cell and nanotechnology applications of C60. C60 grows in a quasi-layer-by-layer mode on a pristine graphite surface and form a special surface structure (coexistence of round and fractal islands). The deposition of Au leads to the formation of a complex array of different surface structures, while the basic island structure of the C60 is preserved. The Au-clusters nucleate preferentially at the graphite-first fullerene layer islands edge forming beadlike structures. A roughness analysis of the fullerene surface indicates the presence of Au atoms embedded in the fullerene surface, situated in the troughs in between the large molecules. The analysis of the spatial and size distributions of Au clusters provides the basis for the development of a qualitative model which describes the relevant surface processes in the Au-fullerene system. The simultaneous deposition of Au and C60 leads to the formation of organized structures, in which Au clusters are embedded in a ring of fullerene molecules with a constant width.

  16. Topochemical 3D polymerization of C60 under high pressure at elevated temperatures.

    PubMed

    Yamanaka, Shoji; Kini, Nagesh S; Kubo, Akira; Jida, Saeko; Kuramoto, Hideaki

    2008-04-02

    Fullerene C60 monomer crystals were compressed to a face-centered cubic (fcc) phase with a lattice parameter of a = 11.93(5) A and a micro-Vickers hardness of 4500 kg/mm2 using high-pressure and high-temperature conditions of 15 GPa at 500-600 degrees C. The hardness is compatible with that of cubic boron nitride (c-BN), suggesting the formation of a 3D C60 polymer. The single-crystal X-ray structural analysis revealed that each C60 molecule in the polymer was linked to the 12 nearest neighbors by [2+2] cycloaddition between the common pentagon-hexagon (56) edges. However, ab initio geometry optimization and molecular dynamics calculations suggested that the 3D polymer should have a rhombohedral structure with the space group of R containing [3+3] cycloaddition between the pentagons of C60 molecules within the plane perpendicular to the 3-fold axis. The higher apparent symmetry of fcc was observed as an averaged structure of different orientations of the rhombohedral structure. The R structure can be derived by only a slight rotation of each C60 unit in the (111) plane of the fcc structure. The band-structure calculation suggested that the 3D polymer (R) was a semiconductor; the activation energy for the electrical conductivity was experimentally determined to be 0.25 eV at 550 K.

  17. Adsorption of 4He on a Single C60

    NASA Astrophysics Data System (ADS)

    Szybisz, L.; Urrutia, I.

    2004-01-01

    The adsorption of $^4$He inside and outside a single fullerene C$_{60}$ is studied. A physisorption potential is proposed. The energetics and structural features of C$_{60}$-$^4$He$_N$ clusters are investigated. Particular attention is paid to the growth of the highly pronounced layered density profile. The evolution towards bulk liquid and surface thickness at the free interface are discussed.

  18. On the action of UV photons on hydrogenated fulleranes C60H36 and C60D36

    NASA Astrophysics Data System (ADS)

    Cataldo, Franco; Iglesias-Groth, Susana

    2009-11-01

    Fulleranes, the hydrogenated fullerenes C60H36 and C60D36 have been synthesized in n-hexane where they show an absorption maximum at 217 nm in their electronic absorption spectra with molar extinction coefficients ɛ217 = 17140 and 16480L cm-1 mol-1, respectively, which correspond to absorption cross-sections of order 6500 Mbarn, about 10 times higher than for C60. We find that the absorption curves measured for these two fulleranes fit well the wavelength, width and shape of the ultraviolet (UV) bump (217 nm) in the extinction curve of the diffuse interstellar medium. If present in the interstellar medium these fulleranes would contribute significantly to the bump extinction, although interstellar carbon budget considerations indicate that C60H36 cannot be the only contributor. The photolysis of fulleranes with monochromatic light at 245 nm causes a shift of the absorption maximum from 217 nm to longer wavelengths. This band shift of the absorption maximum has already been observed in the photolysis or in the thermal processing of hydrogenated carbon dust. The band shift is due to the release of molecular hydrogen, a process which causes the aromatization of the carbon dust. C60H36 and C60D36 are photolyzed at a rate kC60H36 = 2.45 × 10-3 s-1 while kC60D36 = 2.27 × 10-3 s-1. This implies an isotope effect so that C60H36 is photolyzed 1.08 times faster than C60D36. In the interstellar medium, this implies a deuterium enrichment of the hydrogenated interstellar carbon dust. The presence of a measurable isotope effect suggests that the photolysis of C60H36 and C60D36 involves the rupture of the C-H and C-D bond with release of H2. C60H36 releases completely hydrogen when heated to 630°C under inert atmosphere producing back C60 as shown by FT-IR spectroscopy. Thus in the interstellar medium an equilibrium should occur between the hydrogenation of C60 with atomic hydrogen and the emission of molecular hydrogen because of the action of UV photons or thermal

  19. Hydrogen absorption and desorption kinetics in fullerite C60 single crystals. Low-temperature micromechanical and structural characteristics of the interstitial solid solution C60(H2)x

    NASA Astrophysics Data System (ADS)

    Fomenko, L. S.; Lubenets, S. V.; Natsik, V. D.; Stetsenko, Yu. E.; Yagotintsev, K. A.; Strzhemechny, M. A.; Prokhvatilov, A. I.; Osipyan, Yu. A.; Izotov, A. N.; Sidorov, N. S.

    2008-01-01

    The microhardness HV and lattice parameter a of C60 single crystals are measured at room temperature as functions of the hydrogen saturation time t for several values of the saturation temperature (250, 300, and 350°C) at a fixed hydrogen pressure p =30atm. According to the measurements of HV and a, the kinetics of hydrogen absorption is described by a simple exponential law with a single, temperature-dependent characteristic time. In highly saturated samples the microhardness is 4 times greater than for the initial C60 crystal, while the lattice parameter is 0.2% larger. The temperature dependence of the microhardness HV and lattice parameter a of C60(H2)x crystals is investigated in the temperature interval 77-300K. The introduction of hydrogen lowers the temperature of the fcc-sc phase transition, and the transition becomes strongly broadened in temperature. The dependence of the microhardness of the saturated sample on the hold time in air at room temperature is described by the sum of two exponentials with different characteristic times. Kinetics of this kind is presumably due to two processes: desorption of hydrogen from the sample, which causes a decrease of the microhardness, and a simultaneous penetration of gaseous impurities into the sample from the surrounding air, which is accompanied by hardening. The influence of the H2 molecules on the characteristic of the intermolecular interaction in fullerite C60 is discussed and the intercalation-induced processes of dislocation slip and microfracture.

  20. Nonthermal decomposition of C60 polymers induced by tunneling electron injection

    NASA Astrophysics Data System (ADS)

    Nakamura, Yoshiaki; Kagawa, Fumitaka; Kasai, Koichi; Mera, Yutaka; Maeda, Koji

    2004-11-01

    Scanning tunneling microscopic (STM) studies of C60 films deposited on highly oriented pyrolytic graphite substrates revealed that the electron injection from the STM tip induces the decomposition (isomerization) of the C60 molecules that have been polymerized also by the electron injection into the films. Both reaction rates were characterized by a linear dependence on the injected tunneling current and a common threshold around 2 V in the sample bias dependence. We discuss two nonthermal mechanisms for the polymerization and decomposition reactions: electronic excitation mechanism by Auger decay and a hypothetical ionic reaction model.

  1. High-resolution 13C NMR investigation in Cs4C60

    NASA Astrophysics Data System (ADS)

    Goze, C.; Rachdi, F.; Mehring, M.

    1996-08-01

    Four inequivalent carbons were identified by using high-resolution magic angle spinning 13C NMR spectroscopy in Cs4C60. The room temperature NMR spectrum consists of four lines at 214 ppm, 189 ppm, 164 ppm, and 159 ppm, which collapse into a single line at 183 ppm when the sample is heated above 350 K. The intensity of the latter is the sum of the four line intensities. The observed behavior is interpreted in terms of a nonuniform charge and spin distribution on the C60 molecules combined with molecular dynamics.

  2. High resolution NMR studies of one and two dimensional polymerized C60

    NASA Astrophysics Data System (ADS)

    Rachdi, F.; Goze, C.; Hajji, L.; Thier, K. F.; Zimmer, G.; Mehring, M.; Núñez-Regueiro, M.

    We present NMR data of the polymeric phase of em{emvar{A}C_{60}} with em{emvar{A}}=em{K}, em{Rb}, em{Cs}. From the temperature dependent \\isotope{13}{C} line shift of em{RbC_{60}} we have extracted information about the electron density distribution on the em{C_{60}} molecules. The data also support the existence of an \\orbital{sp}{3}{} like bonding type between the molecules. The magnetic phase transition observed at low temperature in em{RbC_{60}} and em{CsC_{60}} is monitored by an increase of the second moment as well as an increase of the spin lattice relaxation rates of the \\isotope{13}{C} and alkali nuclei. The results are compared to \\isotope{13}{C} NMR data of em{KC_{60}} where no signs of a magnetic ordering are found. The magnetically ordered phases are discussed in terms of antiferromagnetic spin density wave. We also report on \\isotope{13}{C} NMR measurements of orthorhombic one dimensional and rhombohedral two dimensional polymers of em{C_{60}} obtained under high pressure. By spinning the samples up to ǎlunit{12}{kHz}, we are able to identify two resonances at ǎlunit{146}{ppm} and ǎlunit{73.5}{ppm} for the orthorhombic polymer and six resonances at ǎlunit*{149.1}{ppm}, ǎlunit*{147.9}{ppm}, ǎlunit*{145.2}{ppm}, ǎlunit*{139.6}{ppm}, ǎlunit*{134.8}{ppm} and ǎlunit{73.5}{ppm} for the rhombohedral one. The static distortion of the em{C_{60}} molecules induced by the transformation under pressure must be at the origin of the observed inequivalent carbons in both systems. The \\isotope{13}{C} NMR lineshape simulations of the obtained spectra are compatible with the suggested polymeric structures where the em{C_{60}} molecules are connected by [2+2] cycloadditions.

  3. 13C and 23Na NMR studies of Na2C60 and Na6C60 fullerides

    NASA Astrophysics Data System (ADS)

    Rachdi, F.; Hajji, L.; Galtier, M.; Yildirim, T.; Fischer, J. E.; Goze, C.; Mehring, M.

    1997-10-01

    We report on 13C and 23Na NMR measurements on Na2C60 and Na6C60 compounds. The room-temperature 13C NMR spectra of Na2C60 and Na6C60 samples present a narrow isotropic line at 172 and 176 ppm, respectively. The Na6C60 resonance is shifted 20 ppm more down field than the resonances of A6C60 compounds with heavier alkalis, indicating a partial charge transfer to the threefold degenerate t1u level which is totally filled in the latter compounds. The 23Na NMR spectrum of A2C60 shows one line at 73 ppm and the one of A6C60 presents two lines at 73 and 147 ppm. The intensity ratio of the latter lines is about 2:1. According to previously reported x-ray data we attribute the line at 147 ppm to the Na tetramers in the octahedral sites and the line at 73 ppm to the Na cations in the tetrahedral ones which are singly occupied.

  4. An experimental and theoretical view of energetic C60 cluster bombardment onto molecular solids.

    PubMed

    Brenes, Daniel A; Postawa, Zbigniew; Wucher, Andreas; Blenkinsopp, Paul; Garrison, Barbara J; Winograd, Nicholas

    2013-01-01

    Recent experimental measurements and calculations performed by molecular dynamics computer simulations indicate, for highly energetic C60 primary ions bombarding molecular solids, the emission of intact molecules is unique. An energy- and angle-resolved neutral mass spectrometer coupled with laser photoionization techniques was used to measure the polar angle distribution of neutral benzo[a]pyrene molecules desorbed by 20-keV [Formula: see text] primary ions and observed to peak at off-normal angles integrated over all possible emission energies. Similarly, computer simulations of 20-keV C60 projectiles bombarding a coarse-grained benzene system resulted in calculations of nearly identical polar angle distributions. Upon resolving the measured and calculated polar angle distributions, sputtered molecules with high kinetic energies are the primary contributors to the off-normal peak. Molecules with low kinetic energies were measured and calculated to desorb broadly peaked about the surface normal. The computer simulations suggest the fast deposition of energy from the C60 impact promotes the molecular emission by fluid-flow and effusive-type motions. The signature of off-normal emission angles is unique for molecules because fragmentation processes remove molecules that would otherwise eject near normal to the surface. Experimental measurements from a Ni {001} single crystal bombarded by 20-keV [Formula: see text] demonstrate the absence of this unique signature.

  5. 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

  6. 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

  7. 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.

  8. Ratio of the surface-enhanced anti-Stokes scattering to the surface-enhanced Stokes-Raman scattering for molecules adsorbed on a silver electrode

    NASA Astrophysics Data System (ADS)

    Brolo, A. G.; Sanderson, A. C.; Smith, A. P.

    2004-01-01

    Surface-enhanced Raman scattering (SERS) from oxazine 720 (oxa), rhodamine 6G (R6G), and pyridine (py) adsorbed on a rough silver surface was observed. The silver electrode was immersed in aqueous solutions permitting control of the potential bias applied to the surface. SERS spectra in the Stokes and anti-Stokes regions were obtained for several applied potentials and two laser excitation energies. Normalized ratios between the anti-Stokes and the Stokes intensities K were calculated from the SERS spectra. The K ratios differed from unity for all the systems investigated. A preferential enhancement of the (surface-enhanced) Stokes scattering was observed for oxa and py. In contrast, the K ratios were higher than unity for R6G, indicating an increase in the anti-Stokes signal. The K ratios measured in this work decreased with the excitation energy and showed a dependence on the energy of the vibrational modes. These results were satisfactorily explained using resonance models, based on the charge-transfer and electromagnetic theories for SERS. No evidence for a SERS-induced nonthermal population distribution among the vibrational states of the adsorbed molecules (vibrational optical pumping) was found. Therefore, we conclude that the main features of the preferential enhancement of the anti-Stokes scattering for an adsorbed molecule on rough silver can be fully understood in the context of current SERS theories.

  9. Silanization of polyelectrolyte-coated particles: an effective route to stabilize Raman tagging molecules adsorbed on micrometer-sized silver particles.

    PubMed

    Kim, Kwan; Lee, Hyang Bong; Shin, Kuan Soo

    2008-06-03

    Micrometer-sized Ag (microAg) powders are very efficient surface-enhanced Raman scattering (SERS) substrates. To use microAg powders as a core material for molecular sensors operating via SERS, it is necessary to stabilize the tagging (i.e., SERS-marker) molecules adsorbed onto them. We demonstrate in this work that once the tagging molecules are coated with aliphatic polyelectrolytes such as poly(allylamine hydrochloride), the base-catalyzed silanization can be readily carried out to form stable silica shells around the polyelectrolyte layers by a biomimetic process; any particle can therefore be coated with silica since polyelectrolytes can be deposited beforehand via a layer-by-layer deposition method. Even after silanization, the SERS peaks of marker molecules on microAg particles are the only observable peaks since aliphatic polyelectrolytes, as well as silica shells, are intrinsically weak Raman scatterers, and more importantly, the SERS signals must be derived mostly from the first layer of the adsorbates (i.e., the marker molecules) in direct contact with the microAg particles. Silica shells, once fabricated, can further be derivatized to possess biofunctional groups; therefore, the modified microAg particles can be used as platforms of highly stable SERS-based biological sensors, as well as barcoding materials.

  10. Dispersion-corrected DFT calculations on C(60)-porphyrin complexes.

    PubMed

    Liao, Meng-Sheng; Watts, John D; Huang, Ming-Ju

    2009-06-07

    The quality of the newly added, empirical dispersion correction in density functional theory (DFT) calculations is examined for several supramolecular complexes of fullerene (C(60)) with free-base and metal porphyrins (Por). The benzene dimer (C(6)H(6))(2), naphthalene dimer (C(10)H(8))(2), and anthracene dimer (C(14)H(10))(2) were also included in the study for comparison. Three density functionals, two damping functions, and two types of basis sets were employed in the computations. The estimated dispersion energies in the fullerene-porphyrin systems are rather large, ranging from 0.5 eV in C(60).ZnP to 1 eV in C(60).H(2)TPP. Any dispersion-corrected DFT (DFT + E(disp)) method is shown to perform well for C(60).H(2)TPP, C(60).ZnTPP, and C(60).ZnP, where the intermolecular distances are relatively large. But large basis sets, e.g. TZP (triple-zeta + one polarization function), are required in order to obtain reliable results with DFT + E(disp). In the case of C(60).FeP, where the intermolecular distance R is short, the DFT + E(disp) calculated R depends on the damping function as well as on the DFT method, and all the DFT + E(disp) calculations lead to significant changes in the relative energies of the various spin states. The quality of the DFT + E(disp) calculated results on C(60).FeP is hard to judge here without detailed experimental data on a C(60).FePor complex. Owing to error cancellation, the pure DFT calculations with a smaller DZP (double-zeta + one polarization function) basis set without any correction are shown to give quite accurate results.

  11. New approach for sensitive photothermal detection of C60 and C70 fullerenes on micro-thin-layer chromatographic plates.

    PubMed

    Suszyński, Zbigniew; Zarzycki, Paweł K

    2015-03-10

    In this paper the pulse thermovision (photothermal) detection and quantification methods of C60 and C70 fullerenes are presented. Quantification results are compared with optical and fluorescence measurements. Target components were separated under isothermal conditions (30 °C) on micro-TLC plates (RP18WF254S) using n-hexane as the mobile phase. The principle of described analytical protocol is based on sensitive measurement of the temperature contrast generated within TLC stationary phase and fullerenes spots after white light pulse excitation. It has been demonstrated that observed temperature contrast is mainly driven by the optical properties of fullerenes (UV-vis absorption spectra). Contrary to the commonly applied optical reflection or transmission techniques the proposed thermovision method involves dissipated light. The results of presented experimental work have revealed that both types of quantitative measurements provide similar outcome despite the key differences in the signal origin. However, it has been found that thermovision method was characterized by smaller value of LOD, particularly for C60 molecule. We demonstrated that application of correlation technique to post-acquisition analysis of the sequence of temperature contrast images significantly increase detection limits of fullerenes, even in comparison to fluorescence quenching detection mode. Moreover, the thermal contrast images and particularly, computed correlation image, allow detection of stationary phase layer nonuniformities, including changes in the adsorbent thickness and thermal conductivity. Therefore, invented pulsed thermovision methodology can be additionally used for fast quality screening of home made and commercially available TLC plates. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Spin-polarization study of CO molecules adsorbed on Fe(110) using metastable-atom deexcitation spectroscopy and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Sun, X.; Förster, S.; Li, Q. X.; Kurahashi, M.; Suzuki, T.; Zhang, J. W.; Yamauchi, Y.; Baum, G.; Steidl, H.

    2007-01-01

    The spin-resolved electronic states of CO molecules adsorbed on Fe(110) surfaces are investigated using spin-polarized metastable-atom deexcitation spectroscopy (SPMDS) measurements and first-principles calculation. The existence of the adsorbate-induced 2π* state, which is partially filled by electron backdonation, is detected directly by SPMDS and reproduced by the calculation of local density of states and subtracted densities. Positive spin asymmetries for 4σ , 5σ/1π , and 2π* peaks observed in SPMDS spectra are well described by the calculated spin density and plane-averaged density of states, which indicate negative-spin polarization towards vacuum side even at the low CO coverage.

  13. Infrared spectroscopy of endohedral HD and D2 in C60

    NASA Astrophysics Data System (ADS)

    Ge, Min; Nagel, U.; Hüvonen, D.; Rõõm, T.; Mamone, S.; Levitt, M. H.; Carravetta, M.; Murata, Y.; Komatsu, K.; Lei, Xuegong; Turro, N. J.

    2011-09-01

    We report on the dynamics of two hydrogen isotopomers, D2 and HD, trapped in the molecular cages of a fullerene C60 molecule. We measured the infrared spectra and analyzed them using a spherical potential for a vibrating rotor. The potential, vibration-rotation Hamiltonian, and dipole moment parameters are compared with previously studied H2@C60 parameters [M. Ge, U. Nagel, D. Hüvonen, T. Rõõm, S. Mamone, M. H. Levitt, M. Carravetta, Y. Murata, K. Komatsu, J. Y.-C. Chen, and N. J. Turro, J. Chem. Phys. 134, 054507 (2011), 10.1063/1.3535598]. The isotropic part of the potential is similar for all three isotopomers. In HD@C60, we observe mixing of the rotational states and an interference effect of the dipole moment terms due to the displacement of the HD rotation center from the fullerene cage center.

  14. Electrical properties of a two-dimensionally hexagonal C60 photopolymer

    NASA Astrophysics Data System (ADS)

    Onoe, J.; Nakayama, T.; Aono, M.; Hara, T.

    2004-07-01

    We investigated the electrical properties of a two-dimensionally (2D) hexagonal C60 photopolymer, using four-probe measurements in air at room temperature. The current-voltage curve shows that the photopolymer exhibits nondoped semiconducting behavior. This behavior is consistent with the theoretical prediction that a 2D hexagonal C60 polymer with a crosslinkage of a [2+2] cycloadditional four-member ring between adjacent C60 molecules is semiconducting [S. Okada and S. Saito, Phys. Rev. B 59, 1930 (1999)]. The origin of these semiconducting properties is discussed on the basis of density-functional calculations for the valence molecular orbitals of the dumbbell C120, which is regarded as a basic unit of the [2+2] crosslinkage of the 2D photopolymer.

  15. Spin frustration and magnetic ordering in the Mott insulating fcc-Cs3C60

    NASA Astrophysics Data System (ADS)

    Kasahara, Yuichi; Takeuchi, Yuki; Itou, Tatsuaki; Iwasa, Yoshihiro; Arcon, Denis; Rosseinsky, Matthew; Prassides, Kosmas

    2014-03-01

    The low-temperature magnetic state at ambient pressure has been investigated by specific heat and nuclear magnetic resonance (NMR) measurements in face-centered-cubic (fcc-) Cs3C60, which is characterized by a Mott insulating state with S = 1 / 2 spins in C603- anions and a geometrical spin frustration inherent in the fcc lattice. Specific heat exhibited no sharp anomaly down to 0.4 K, but both magnetic specific heat and NMR relaxation rate revealed a broad peak around 2.5 K, indicating that the reported antiferromagnetic ordering is accompanied by a gradual freezing of electronic spins with distributed transition temperatures. These results are unexpected in the conventional fcc antiferromagnets. Interplay of geometrical frustration, orientational disorder of C60 molecules, and weak Mottness gives rise to the unique magnetic ground state in fcc-Cs3C60.

  16. Photocatalytic C60-amorphous TiO2 composites prepared by atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Justh, Nóra; Firkala, Tamás; László, Krisztina; Lábár, János; Szilágyi, Imre Miklós

    2017-10-01

    Nanocomposites of TiO2 and single fullerene (C60) molecule are prepared by atomic layer deposition (ALD). To create nucleation sites for the ALD reaction, the bare fullerene is functionalized by H2SO4/HNO3 treatment, which results in C60-SO3H. After a NaOH washing step the intermediate hydrolyzes into C60sbnd OH. This process and the consecutive ALD growth of TiO2 are monitored with FTIR, TG/DTA-MS, EDX, Raman, FTIR, XRD, and TEM measurements. Although the TiO2 grown by ALD at 80 and 160 °C onto fullerol is amorphous it enhances the decomposition of methyl orange under UV exposure. This study proves that amorphous TiO2 grown by low temperature ALD has photocatalytic activity, and it can be used e.g. as self-cleaning coatings also on heat sensitive substrates.

  17. 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.

  18. Computational study of enantioselective interaction between C60 fullerene and its derivatives with L-histidine.

    PubMed

    Lal, Bhajan

    2007-04-01

    The mechanism of the enantioselective binding of L-histidine with C(60) fullerene and its derivatives, (1,2-methanofullerene C(60))-61-carboxylic acid, diethyl (1,2-methanofullerene C(60))-61-61-dicarboxylate and tert-butyl (1,2-methanofullerene C(60))-61-carboxylate based chiral selectors was studied by quantum chemical calculations. All the molecules were fully optimized at RHF/6-31G* basis set. Relative energies between the different complexes were subsequently estimated with single-point electronic energies computed using Møller-Plesset perturbation theory (MP2). Stability and feasibility of all the generated structures were supported by their respective energy minima and fundamental frequencies. It was observed that interaction of fullerene derivatives with L-histidine is due to the existence of hydrogen bonding forces during the complex formation. The intermolecular forces, flow of atomic charges, binding energy, hardness, dipole moment and localization of electrostatic potential are in agreement with enantioselective interaction of L-histidine with C(60) fullerene and its derivatives. It is found that theoretical evaluation to be consistent with the experimental data.

  19. 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.

  20. 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...

  1. Production of C59N:C60 solid solution

    NASA Astrophysics Data System (ADS)

    Fülöp, Ferenc; Rockenbauer, Antal; Simon, Ferenc; Pekker, Sándor; Korecz, László; Garaj, Slaven; Jánossy, András

    2001-10-01

    We describe a simple way to produce large quantities of solid solutions of monomer C59N in pure C60 using an electric gas discharge tube. Typical concentrations are 10-5 to 10-4 C59N with respect to C60. The 14N and several 13C hyperfine constants were measured by ESR. These are a sensitive test for electronic structure calculations of the monomer. As the temperature is raised towards the sc to fcc structural transition at 261 K, the ESR spectrum motionally narrows and the activation energy for reorientation is measured. The rotational dynamics of the C59N monomer between 130 and 600 K parallels that of C60 in the bulk thus interactions between C59N and C60 are surprisingly weak.

  2. 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...

  3. 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)

  4. Superintermolecular orbitals in the C60-pentacene complex

    NASA Astrophysics Data System (ADS)

    Zhang, G. P.; Gardner, A.; Latta, T.; Drake, K.; Bai, Y. H.

    2016-12-01

    We report a group of unusually big molecular orbitals in the C60-pentacene complex. Our first-principles density-functional calculation shows that these orbitals are very delocalized and cover both C60 and pentacene, which we call superintermolecular orbitals (SIMOs). Their spatial extension can reach 1 nm or larger. Optically, SIMOs are dark. Different from ordinary unoccupied molecular orbitals, SIMOs have a very weak Coulomb and exchange interaction. Their energy levels are very similar to the native superatomic molecular orbitals in C60and can be approximately characterized by orbital angular momentum quantum numbers. They have a distinctive spatial preference. These features fit the key characters of charge-generation states that channel initially bound electrons and holes into free-charge carriers. Thus, our finding is important for C60-pentacene photovoltaics.

  5. 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)

  6. Electrical conductivity of polyazomethine/fullerene C60 nanocomposites

    NASA Astrophysics Data System (ADS)

    Bronnikov, Sergei; Podshivalov, Aleksandr; Kostromin, Sergei; Asandulesa, Mihai; Cozan, Vasile

    2017-02-01

    We prepared the polyazomethine/fullerene C60 nanocomposites varying in C60 loading. With a broadband dielectric relaxation spectrometer, we measured their electrical conductivity σm being a sum of dc conductivity σdc and ac conductivity σac. A small C60 content (0.25 and 0.5 wt.%) was shown to decrease σdc, whereas a larger amount of C60 (2.5 wt.%) was found to increase σdc of the nanocomposite. The temperature dependences of σac were described with the Arrhenius equation, while the frequency dependences of σac were characterized with a power function. The correlated barrier hopping was accepted as the most suitable mechanism to explain the σac behavior of the nanocomposites.

  7. Optical limiting behavior of C 60 doped ethylenepropylenediene polymethylene polymer

    NASA Astrophysics Data System (ADS)

    Zidan, M. D.; Ajji, Z.; Allaf, A. W.; Allahham, A.

    2010-06-01

    Optical limiting measurements on C 60 in toluene-ethylenepropylenediene polymethylene (EPDM) polymer blends and in EPDM polymer films at three different concentrations have been carried out. The measurements were undertaken using 532 nm wavelength, 10 ns pulses from a frequency-doubled Nd-YAG Laser. The results show that the optical limiting efficiency is concentration dependent and that the limiting efficiency for C 60 in toluene-EPDM polymer blends is better than in EPDM polymer film samples.

  8. 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.

  9. Conjugated Porphyrin Dimers: Cooperative Effects and Electronic Communication in Supramolecular Ensembles with C60.

    PubMed

    Moreira, Luis; Calbo, Joaquín; Aragó, Juan; Illescas, Beatriz M; Nierengarten, Iwona; Delavaux-Nicot, Béatrice; Ortí, Enrique; Martín, Nazario; Nierengarten, Jean-François

    2016-11-30

    Two new conjugated porphyrin-based systems (dimers 3 and 4) endowed with suitable crown ethers have been synthesized as receptors for a fullerene-ammonium salt derivative (1). Association constants in solution have been determined by UV-vis titration experiments in CH2Cl2 at room temperature. The designed hosts are able to associate up to two fullerene-based guest molecules and present association constants as high as ∼5 × 10(8) M(-1). Calculation of the allosteric cooperative factor α for supramolecular complexes [3·12] and [4·12] showed a negative cooperative effect in both cases. The interactions accounting for the formation of the associates are based, first, on the complementary ammonium-crown ether interaction and, second, on the π-π interactions between the porphyrin rings and the C60 moieties. Theoretical calculations have evidenced a significant decrease of the electron density in the porphyrin dimers 3 and 4 upon complexation of the first C60 molecule, in good agreement with the negative cooperativity found in these systems. This negative effect is partially compensated by the stabilizing C60-C60 interactions that take place in the more stable syn-disposition of [4·12].

  10. Density functional investigation of CO and NO adsorption on TM-decorated C60 fullerene

    NASA Astrophysics Data System (ADS)

    El Mahdy, A. M.

    2016-10-01

    We have analysed the adsorptions of CO and NO molecules on pristine, TM (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn) in TM-doped fullerene C60 by using density functional theory (DFT) calculations at B3LYP/6-31g(d) theoretical level. This work revealed that the transition metal doped fullerenes were more highly sensitive to CO and NO adsorption than that of pure fullerene C60. The Fe-doped fullerenes C60 displayed the strongest interaction with C and N atoms of CO and NO molecules respectively. The nature of charge transfer between the d-orbitals of TM, and the π* orbital of the nearby C and N of CO and NO are clarified. Natural bond orbital (NBO) analysis reveals that the electronic configuration of the doped TM metal represents a qualitative change with respect to that of the free-metal. The binding of CO and NO precursor is mostly dominated by the metal E (i) (XO ..TM) pairwise additive contributions, and the role of the C60 is not restricted to supporting the metal.

  11. The effect of incident angle on the C 60+ bombardment of molecular solids

    NASA Astrophysics Data System (ADS)

    Kozole, Joseph; Willingham, David; Winograd, Nicholas

    2008-12-01

    The effect of incident angle on the quality of SIMS molecular depth profiling using C 60+ was investigated. Cholesterol films of ˜300 nm thickness on Si were employed as a model and were eroded using 40 keV C 60+ at an incident angle of 40° and 73° with respect to the surface normal. The erosion process was characterized by determining at each angle the relative amount of chemical damage, the total sputtering yield of cholesterol molecules, and the interface width between the film and the Si substrate. The results show that there is less molecule damage at an angle of incidence of 73° and that the total sputtering yield is largest at an angle of incidence of 40°. The measurements suggest reduced damage is not necessarily dependent upon enhanced yields and that depositing the incident energy nearer the surface by using glancing angles is most important. The interface width parameter supports this idea by indicating that at the 73° incident angle, C 60+ produces a smaller altered layer depth. Overall, the results show that 73° incidence is the better angle for molecular depth profiling using 40 keV C 60+.

  12. Conjugated Porphyrin Dimers: Cooperative Effects and Electronic Communication in Supramolecular Ensembles with C60

    PubMed Central

    2016-01-01

    Two new conjugated porphyrin-based systems (dimers 3 and 4) endowed with suitable crown ethers have been synthesized as receptors for a fullerene-ammonium salt derivative (1). Association constants in solution have been determined by UV–vis titration experiments in CH2Cl2 at room temperature. The designed hosts are able to associate up to two fullerene-based guest molecules and present association constants as high as ∼5 × 108 M–1. Calculation of the allosteric cooperative factor α for supramolecular complexes [3·12] and [4·12] showed a negative cooperative effect in both cases. The interactions accounting for the formation of the associates are based, first, on the complementary ammonium-crown ether interaction and, second, on the π–π interactions between the porphyrin rings and the C60 moieties. Theoretical calculations have evidenced a significant decrease of the electron density in the porphyrin dimers 3 and 4 upon complexation of the first C60 molecule, in good agreement with the negative cooperativity found in these systems. This negative effect is partially compensated by the stabilizing C60C60 interactions that take place in the more stable syn-disposition of [4·12]. PMID:27640915

  13. 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

    2015-02-05

    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. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. High-T C superconductivity in Cs3C60 compounds governed by local Cs-C60 Coulomb interactions

    NASA Astrophysics Data System (ADS)

    Harshman, Dale R.; Fiory, Anthony T.

    2017-04-01

    Unique among alkali-doped A 3C60 fullerene compounds, the A15 and fcc forms of Cs3C60 exhibit superconducting states varying under hydrostatic pressure with highest transition temperatures at T\\text{C}\\text{meas}   =  38.3 and 35.2 K, respectively. Herein it is argued that these two compounds under pressure represent the optimal materials of the A 3C60 family, and that the C60-associated superconductivity is mediated through Coulombic interactions with charges on the alkalis. A derivation of the interlayer Coulombic pairing model of high-T C superconductivity employing non-planar geometry is introduced, generalizing the picture of two interacting layers to an interaction between charge reservoirs located on the C60 and alkali ions. The optimal transition temperature follows the algebraic expression, T C0  =  (12.474 nm2 K)/ℓζ, where ℓ relates to the mean spacing between interacting surface charges on the C60 and ζ is the average radial distance between the C60 surface and the neighboring Cs ions. Values of T C0 for the measured cation stoichiometries of Cs3-x C60 with x  ≈  0 are found to be 38.19 and 36.88 K for the A15 and fcc forms, respectively, with the dichotomy in transition temperature reflecting the larger ζ and structural disorder in the fcc form. In the A15 form, modeled interacting charges and Coulomb potential e2/ζ are shown to agree quantitatively with findings from nuclear-spin relaxation and mid-infrared optical conductivity. In the fcc form, suppression of T\\text{C}\\text{meas} below T C0 is ascribed to native structural disorder. Phononic effects in conjunction with Coulombic pairing are discussed.

  15. High-T C superconductivity in Cs3C60 compounds governed by local Cs-C60 Coulomb interactions.

    PubMed

    Harshman, Dale R; Fiory, Anthony T

    2017-04-12

    Unique among alkali-doped A 3C60 fullerene compounds, the A15 and fcc forms of Cs3C60 exhibit superconducting states varying under hydrostatic pressure with highest transition temperatures at [Formula: see text]  =  38.3 and 35.2 K, respectively. Herein it is argued that these two compounds under pressure represent the optimal materials of the A 3C60 family, and that the C60-associated superconductivity is mediated through Coulombic interactions with charges on the alkalis. A derivation of the interlayer Coulombic pairing model of high-T C superconductivity employing non-planar geometry is introduced, generalizing the picture of two interacting layers to an interaction between charge reservoirs located on the C60 and alkali ions. The optimal transition temperature follows the algebraic expression, T C0  =  (12.474 nm(2) K)/ℓζ, where ℓ relates to the mean spacing between interacting surface charges on the C60 and ζ is the average radial distance between the C60 surface and the neighboring Cs ions. Values of T C0 for the measured cation stoichiometries of Cs3-x C60 with x  ≈  0 are found to be 38.19 and 36.88 K for the A15 and fcc forms, respectively, with the dichotomy in transition temperature reflecting the larger ζ and structural disorder in the fcc form. In the A15 form, modeled interacting charges and Coulomb potential e(2)/ζ are shown to agree quantitatively with findings from nuclear-spin relaxation and mid-infrared optical conductivity. In the fcc form, suppression of [Formula: see text] below T C0 is ascribed to native structural disorder. Phononic effects in conjunction with Coulombic pairing are discussed.

  16. Electron-paramagnetic-resonance scattering rates in metallic RbC60 and CsC60

    NASA Astrophysics Data System (ADS)

    Rahmer, J.; Grupp, A.; Mehring, M.

    2001-12-01

    We derive conduction-electron scattering rates in the metallic polymer phase of RbC60 and CsC60 from the investigation of the temperature-dependent conduction electron-spin-resonance linewidth at X- (9 GHz) and W-band (94 GHz) frequencies by applying the Elliott theory. We obtain scattering rates that favor an essentially isotropic electronic structure of the polymer phase.

  17. Comparative analysis of two aqueous-colloidal solutions of C 60 fullerene with help of FTIR reflectance and UV-Vis spectroscopy

    NASA Astrophysics Data System (ADS)

    Andrievsky, G. V.; Klochkov, V. K.; Bordyuh, A. B.; Dovbeshko, G. I.

    2002-09-01

    Two types of fullerene-water colloidal systems: molecular-colloidal C 60 solution in water (C 60FWS) and typical monodisperse C 60 hydrosol are compared in this work. It was confirmed that C 60FWS consists of isolated C 60 molecules in hydrated state, C 60@{H 2O} n, and of their small spherical C 60 clusters of different sizes. It was shown that C 60FWS simultaneously has the properties of both true solutions and colloidal systems. The origin of supramolecular complexes C 60@{H 2O} n stabilization is explained both by the weak donor-acceptor interactions of unpaired electrons of H 2O oxygen atoms with fullerene molecule and by formation of ordered, H-bounded and sphere-like hydrated shells around the fullerene. Spectra of surface enhanced infrared absorption (SEIRA) of C 60 on gold substrate were recorded in FTIR reflectance mode. In the 400-900 cm -1 region some additional vibration bands of C 60, which are forbidden in IR spectra, have been registered. Earlier the similar bands had been observed in inelastic neutron scattering.

  18. How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO2 nanoparticles? A quasi-elastic neutron scattering study

    PubMed Central

    Vaissier, Valerie; Sakai, Victoria Garcia; Li, Xiaoe; Cabral, João T.; Nelson, Jenny; Barnes, Piers R. F.

    2016-01-01

    Motions of molecules adsorbed to surfaces may control the rate of charge transport within monolayers in systems such as dye sensitized solar cells. We used quasi-elastic neutron scattering (QENS) to evaluate the possible dynamics of two small dye moieties, isonicotinic acid (INA) and bis-isonicotinic acid (BINA), attached to TiO2 nanoparticles via carboxylate groups. The scattering data indicate that moieties are immobile and do not rotate around the anchoring groups on timescales between around 10 ps and a few ns (corresponding to the instrumental range). This gives an upper limit for the rate at which conformational fluctuations can assist charge transport between anchored molecules. Our observations suggest that if the conformation of larger dye molecules varies with time, it does so on longer timescales and/or in parts of the molecule which are not directly connected to the anchoring group. The QENS measurements also indicate that several layers of acetonitrile solvent molecules are immobilized at the interface with the TiO2 on the measurement time scale, in reasonable agreement with recent classical molecular dynamics results. PMID:27991538

  19. How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO2 nanoparticles? A quasi-elastic neutron scattering study

    NASA Astrophysics Data System (ADS)

    Vaissier, Valerie; Sakai, Victoria Garcia; Li, Xiaoe; Cabral, João T.; Nelson, Jenny; Barnes, Piers R. F.

    2016-12-01

    Motions of molecules adsorbed to surfaces may control the rate of charge transport within monolayers in systems such as dye sensitized solar cells. We used quasi-elastic neutron scattering (QENS) to evaluate the possible dynamics of two small dye moieties, isonicotinic acid (INA) and bis-isonicotinic acid (BINA), attached to TiO2 nanoparticles via carboxylate groups. The scattering data indicate that moieties are immobile and do not rotate around the anchoring groups on timescales between around 10 ps and a few ns (corresponding to the instrumental range). This gives an upper limit for the rate at which conformational fluctuations can assist charge transport between anchored molecules. Our observations suggest that if the conformation of larger dye molecules varies with time, it does so on longer timescales and/or in parts of the molecule which are not directly connected to the anchoring group. The QENS measurements also indicate that several layers of acetonitrile solvent molecules are immobilized at the interface with the TiO2 on the measurement time scale, in reasonable agreement with recent classical molecular dynamics results.

  20. Direct demonstration for changes in surface plasmon resonance induced by surface-enhanced Raman scattering quenching of dye molecules adsorbed on single Ag nanoparticles

    NASA Astrophysics Data System (ADS)

    Itoh, Tamitake; Hashimoto, Kazuhiro; Ikehata, Akifumi; Ozaki, Yukihiro

    2003-12-01

    Changes in surface plasmon resonance (SPR) bands induced by surface-enhanced Raman scattering (SERS) quenching of rhodamine 6G (R6G) molecules adsorbed on single Ag nanoparticles were investigated by light scattering microspectroscopy. It was found that SPR bands show a peak shift to a higher-energy side and that their intensities increase after SERS quenching. It was also revealed that these SPR bands are accompanied by an enhanced absorption band of R6G and that it has the same anisotropy as SERS and SPR bands. Assuming that the changes in the SPR bands are caused by the desorption of R6G molecules, we compared our experimental findings with calculation results obtained based on Rayleigh scattering theory.

  1. Dipole polarizability, sum rules, mean excitation energies, and long-range dispersion coefficients for buckminsterfullerene C 60

    NASA Astrophysics Data System (ADS)

    Kumar, Ashok; Thakkar, Ajit J.

    2011-11-01

    Experimental photoabsorption cross-sections combined with constraints provided by the Kuhn-Reiche-Thomas sum rule and the high-energy behavior of the dipole-oscillator-strength density are used to construct dipole oscillator strength distributions for buckminsterfullerene (C60). The distributions are used to predict dipole sum rules Sk, mean excitation energies Ik, the frequency dependent polarizability, and C6 coefficients for the long-range dipole-dipole interactions of C60 with a variety of atoms and molecules.

  2. Stable compounds of helium and neon: he@c60 and ne@c60.

    PubMed

    Saunders, M; Jiménez-Vázquez, H A; Cross, R J; Poreda, R J

    1993-03-05

    It is demonstrated that fullerenes, prepared via the standard method (an arc between graphite electrodes in a partial pressure of helium), on heating to high temperatures release (4)He and (3)He. The amount corresponds to one (4)He for every 880,000 fullerene molecules. The (3)He/(4)He isotopic ratio is that of tank helium rather than that of atmospheric helium. These results convincingly show that the helium is inside and that there is no exchange with the atmosphere. The amount found corresponds with a prediction from a simple model based on the expected volume of the cavity. In addition, the temperature dependence for the release of helium implies a barrier about 80 kilocalories per mole. This is much lower than the barrier expected from theory for helium passing through one of the rings in the intact structure. Amechanism involving reversibly breaking one or more bonds to temporarily open a "window" in the cage is proposed. A predicted consequence of this mechanism is the incorporation of other gases while the "window" is open. This was demonstrated through the incorporation of (3)He and neon by heating fullerene in their presence.

  3. 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

  4. 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).

  5. Physical properties of highly-oriented rhombohedral C60 polymer

    NASA Astrophysics Data System (ADS)

    Tokumoto, M.; Narymbetov, B.; Kobayashi, H.; Makarova, T. L.; Davydov, V. A.; Rakhmania, A. V.; Kashevarova, L. S.

    2000-11-01

    Rhombohedral phase of pressure-temperature treated C60 polymer was investigated by resistivity, X-ray diffraction and ESR measurements. The pure rhombohedral phase of C60 polymer displays highly anisotropic electrical properties, and the conductivity in the polymerized 2D plane exhibits a metallic feature with weak localization. X-ray diffraction measurements have revealed that the diffraction patterns are essentially anisotropic. We have carried out the scanning of a reciprocal space in order to reveal the distribution of diffraction intensities. The result testifies to the high degree of mutual orientations of crystallites in the sample not only along the [001] direction but also in the (001) plane. Apparently the observed mosaicity of the crystal is connected with the highly anisotropic electrical properties of the rhombohedral phase of pressure-treated C60 polymer. A Dysonian ESR absorption lineshape consistent with the metallic nature was observed.

  6. 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.

  7. A search for C60 in carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

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

    1993-02-01

    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.

  8. Growth mechanism of silicon carbide films on silicon substrates using C 60 carbonization

    NASA Astrophysics Data System (ADS)

    Chen, Dong; Workman, Richard; Sarid, Dror

    1995-12-01

    Silicon carbide films were grown on silicon substrates using C 60 molecules as a carbon source. The grown films were characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and infrared spectroscopy (IRS). Also, using SiO 2 as a mask on the Si substrate, a patterned SiC film was grown. Growth and defect mechanisms are discussed and compared with conventional CVD carbidizing methods.

  9. Symmetry of C60 and a Force Constant Model for Vibrational Modes

    NASA Astrophysics Data System (ADS)

    Koç, Ramazan; Tütüncüler, Hayriye

    1998-02-01

    A force-constant model for the vibrational modes in C60 is presented. The Keating type potential is adopted for calculating the dynamical matrix. Using symmetries of the molecule, the dynamical matrix which yields the vibrational modes is block-diagonalized. We summarize the role of group theory in specifying the vibrational modes. The results are in excellent agreement with experiments. The effect of bond-stretching force constants on the vibrational modes will be presented.

  10. Tunneling anisotropic magnetoresistance in C60-based organic spintronic systems

    NASA Astrophysics Data System (ADS)

    Wang, K.; Sanderink, J. G. M.; Bolhuis, T.; van der Wiel, W. G.; de Jong, M. P.

    2014-05-01

    C60 fullerenes are interesting molecular semiconductors for spintronics since they exhibit weak spin-orbit and hyperfine interactions, which is a prerequisite for long spin lifetimes. We report spin-polarized transport in spin-valve-like structures containing ultrathin (<10 nm) C60 layers, ferromagnetic (FM) epitaxial face-centered-cubic (fcc) Co (111) contacts, AlOx tunnel barriers, and nonmagnetic Al counter electrodes. Even though genuine spin-valve behavior cannot occur for only one FM contact, we find significant tunneling anisotropic magnetoresistance (TAMR) upon rotating the in-plane magnetization, originating from spin-orbit interaction (SOI) induced anisotropy of the fcc (111) Co bands. The uniaxial magnetocrystalline anisotropy of the Co electrodes results in a predominantly twofold symmetric in-plane TAMR effect. We investigated the TAMR effect in the direct tunneling regime (2 nm C60), at the transition point to two-step tunneling (4 nm C60), and in the multistep regime (8 nm C60). A sizable TAMR of 4.5% is found at 5 K under application of a 500-mT in-plane magnetic field for C60 layers of 2 nm, which is strongly suppressed at 8 nm thickness, indicating that TAMR may strongly contribute to the "spin-valve" signal for direct tunneling, but not for multistep tunneling. The TAMR effect is proposed to be due to a combination of SOI induced modulation of the tunneling DOS upon rotating the in-plane magnetization of the fcc epitaxial Co thin film, resonant tunneling processes involving interfacial states, and different Bychkov-Rashba SOI at the different interfaces.

  11. Can the state of platinum species be unambiguously determined by the stretching frequency of an adsorbed CO probe molecule?

    PubMed

    Aleksandrov, Hristiyan A; Neyman, Konstantin M; Hadjiivanov, Konstantin I; Vayssilov, Georgi N

    2016-08-10

    The paper addresses possible ambiguities in the determination of the state of platinum species by the stretching frequency of a CO probe, which is a common technique for characterization of platinum-containing catalytic systems. We present a comprehensive comparison of the available experimental data with our theoretical modeling (density functional) results of pertinent systems - platinum surfaces, nanoparticles and clusters as well as reduced or oxidized platinum moieties on a ceria support. Our results for CO adsorbed on-top on metallic Pt(0), with C-O vibrational frequencies in the region 2018-2077 cm(-1), suggest that a decrease of the coordination number of the platinum atom, to which CO is bound, by one lowers the CO frequency by about 7 cm(-1). This trend corroborates the Kappers-van der Maas correlation derived from the analysis of the experimental stretching frequency of CO adsorbed on platinum-containing samples on different supports. We also analyzed the effect of the charge of platinum species on the CO frequency. Based on the calculated vibrational frequencies of CO in various model systems, we concluded that the actual state of the platinum species may be mistaken based only on the measured value of the C-O vibrational frequency due to overlapping regions of frequencies corresponding to different types of species. In order to identify the actual state of platinum species one has to combine this powerful technique with other approaches.

  12. Chemical effects in C 60 irradiation of polymers

    NASA Astrophysics Data System (ADS)

    Möllers, R.; Tuccitto, N.; Torrisi, V.; Niehuis, E.; Licciardello, A.

    2006-07-01

    The C 60 erosion behaviour of poly(methyl)methacrylate (PMMA), poly(α-methyl)styrene (PAMS) and polystyrene (PS) has been studied at various temperatures and compared with that under Ga + irradiation. Strong variations of erosion yields are observed, indicating that chemical degradation mechanisms are operating. In particular, our results suggest that fast depolymerization mechanisms are important in leaving the surface of the sputter crater virtually undamaged. Since such mechanisms are connected with the chemical nature of the polymer, the possibility of performing molecular depth profiling of polymers with C 60 appears to depend strongly on the chemical nature of the system under study.

  13. Electronic structure and optical properties of solid C 60

    NASA Astrophysics Data System (ADS)

    Mattesini, M.; Ahuja, R.; Sa, L.; Hugosson, H. W.; Johansson, B.; Eriksson, O.

    2009-06-01

    The electronic structure and the optical properties of face-centered-cubic C 60 have been investigated by using an all-electron full-potential method. Our ab initio results show that the imaginary dielectric function for high-energy values looks very similar to that of graphite, revealing close electronic structure similarities between the two systems. We have also identified the origin of different peaks in the dielectric function of fullerene by means of the calculated electronic density of states. The computed optical spectrum compares fairly well with the available experimental data for the Vis-UV absorption spectrum of solid C 60.

  14. 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.

  15. Supramolecular structures and photoelectronic properties of the inclusion complex of a cyclic free-base porphyrin dimer and C60.

    PubMed

    Nobukuni, Hirofumi; Shimazaki, Yuichi; Uno, Hidemitsu; Naruta, Yoshinori; Ohkubo, Kei; Kojima, Takahiko; Fukuzumi, Shunichi; Seki, Shu; Sakai, Hayato; Hasobe, Taku; Tani, Fumito

    2010-10-11

    A cyclic free-base porphyrin dimer H4-CPD(Py) (CPD = cyclic porphyrin dimer) linked by butadiyne moieties bearing 4-pyridyl groups self-assembles to form a novel porphyrin nanotube in the crystalline state. The cyclic molecules link together through nonclassical C-H⋅⋅⋅N hydrogen bonds and π–π interactions of the pyridyl groups along the crystallographic a axis. H4-CPD(Py) includes a C60 molecule in its cavity in solution. In the crystal structure of the inclusion complex (C60⊂H4-CPD(Py)), the dimer “bites” a C60 molecule by tilting the porphyrin rings with respect to each other, and there are strong π–π interactions between the porphyrin rings and C60. The included C60 molecules form a zigzag chain along the crystallographic b axis through van der Waals contacts with each other. Femtosecond laser flash photolysis of C60⊂H4-CPD(Py) in the solid state with photoexcitation at 420 nm shows the formation of a completely charge-separated state {H4-CPD(Py)·+ + C60·−}, which decays with a lifetime of 470 ps to the ground state. The charge-carrier mobility of the single crystal of C60⊂H4-CPD(Py) was determined by flash photolysis time-resolved microwave conductivity (FP-TRMC) measurements. C60⊂H4-CPD(Py) has an anisotropic charge mobility (Σμ = 0.16 and 0.13 cm2 V(−1)  s(−1)) along the zigzag chain of C60 (which runs at 45° and parallel to the crystallographic b axis). To construct a photoelectrochemical cell, C60⊂H4-CPD(Py) was deposited onto nanostructured SnO2 films on a transparent electrode. The solar cell exhibited photovoltaic activity with an incident photon to current conversion efficiency of 17%. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Low-temperature scanning tunneling microscopy/ultraviolet photoelectron spectroscopy investigation of two-dimensional crystallization of C60: pentacence binary system on Ag(111)

    NASA Astrophysics Data System (ADS)

    Lin Zhang, Jia; Hong Liang Zhang, Kelvin; Qiang Zhong, Jian; Chao Niu, Tian; Chen, Wei

    2012-02-01

    Atomic scale investigation of temperature-dependent two-dimensional (2 D) crystallization processes of fullerene-C60 on pentacene-covered Ag(111) surface has been carried out by in situ low-temperature scanning tunneling microscopy (LT-STM) experiments. To evaluate the effect of molecule-substrate interfacial interactions on the 2 D crystallization of C60: pentacene binary system, we also carried out the same self-assembly experiments of C60 on monolayer pentacene covered graphite substrate. It is revealed that temperature-dependent structural transition of various ordered C60 nanoassemblies is strongly influenced by the molecule-Ag(111) interfacial interactions, and further mediated by the weak C60-pentacene intermolecular interactions. In situ ultraviolet photoelectron spectroscopy (UPS) has been used to evaluate the nature of the intermolecular interactions between C60 and pentacene films.

  17. Different contact formations at the interfaces of C60/LiF/Al and C60/LiF/Ag

    NASA Astrophysics Data System (ADS)

    Jeon, Pyungeun; Kang, Seong Jun; Lee, Hyunbok; Lee, Jeihyun; Jeong, Kwangho; Lee, JinWoo; Yi, Yeonjin

    2012-04-01

    C60 has been used as an electron accepting and transporting material in various organic electronic devices. In such devices, Al and Ag have been adopted as a common cathode in combination with electron injection layers (EIL), e.g., LiF. We found that the initial interface formations of C60/LiF/Al and C60/LiF/Ag are quite different in terms of interfacial electronic structures. We measured the interfacial electronic structures with photoemission spectroscopy and found that LiF works well as an EIL on Al but performs poorly on Ag. The origin of this difference could be attributed to the larger interface dipole on Al, highlighting the importance of the choice of cathode materials.

  18. Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials

    PubMed Central

    Song, Wenwu; Shi, Jianwei

    2017-01-01

    Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite’s chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface. PMID:28301544

  19. Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials.

    PubMed

    Qi, Xuejun; Song, Wenwu; Shi, Jianwei

    2017-01-01

    Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite's chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface.

  20. Molecular depth profiling in ice matrices using C 60 projectiles

    NASA Astrophysics Data System (ADS)

    Wucher, A.; Sun, S.; Szakal, C.; Winograd, N.

    2004-06-01

    The prospects of molecular sputter depth profiling using C 60+ projectiles were investigated on thick ice layers prepared by freezing aqueous solutions of histamine onto a metal substrate. The samples were analyzed in a ToF-SIMS spectrometer equipped with a liquid metal Ga + ion source and a newly developed fullerene ion source. The C 60+ beam was used to erode the surface, while static ToF-SIMS spectra were taken with both ion beams alternatively between sputtering cycles. We find that the signals both related to the ice matrix and to the histamine are about two orders of magnitude higher under 20-keV C 60 than under 15-keV Ga bombardment. Histamine related molecular signals are found to increase drastically if the freshly introduced surface is pre-sputtered with C 60 ions, until at a total ion fluence of about 10 13 cm -2 the spectra are completely dominated by the molecular ion and characteristic fragments of histamine. At larger fluence, the signal is found to decrease with a disappearance cross section of approximately 10 -14 cm 2, until at total fluences of about 10 14 cm -2 a steady state with stable molecular signals is reached. In contrast, no appreciable molecular signal could be observed if Ga + ions were used to erode the surface.

  1. Confirmation of C60 in the Reflection Nebula NGC 7023

    NASA Astrophysics Data System (ADS)

    Sellgren, K.; Werner, M. W.; Ingalls, J. G.; Smith, J. D. T.; Carleton, T. M.; Joblin, C.

    2011-03-01

    The fullerene C60 has four infrared active vibrational transitions at 7.0, 8.5, 17.5 and 18.9 μm. We have previously observed emission features at 17.4 and 18.9 μm in the reflection nebula NGC 7023 and demonstrated spatial correlations suggestive of a common origin. We now confirm the identification of these features with C60 by detecting a third emission feature at 7.04 ± 0.05μm at a position of strong 18.9 μm emission in NGC 7023. We also report the detection of these three features in the reflection nebula NGC 2023. We show with spectroscopic mapping of NGC 7023 that the 18.9 μm feature peaks on the central star, that the 16.4 μm emission feature due to PAHs peaks between the star and a nearby photodissociation front, and that the 17.4 μm feature is a blend of a PAH feature and C60. The derived C60 abundance is consistent with that from previous upper limits and possible fullerene detections in the interstellar medium.

  2. 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.

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

    PubMed

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

    2010-09-03

    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.

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

    PubMed

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

    2012-05-02

    A one-dimensional (1D) uneven peanut-shaped C(60) polymer formed from electron-beam (EB)-induced polymerization of C(60) 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 C(60) 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 C(60) 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. © 2012 IOP Publishing Ltd

  5. 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.

  6. 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.

  7. Effects of aqueous stable fullerene nanocrystal (nC60) on copper (trace necessary nutrient metal): Enhanced toxicity and accumulation of copper in Daphnia magna.

    PubMed

    Tao, Xianji; He, Yiliang; Fortner, John D; Chen, Yongsheng; Hughes, Joseph B

    2013-08-01

    Our focus herein is to evaluate the potential interaction between nC60 and copper, a trace necessary metal, in light of the impact on toxicity. The non-observable effects concentration (NOEC) of nC60 was confirmed as 100μgL(-1) before. When Daphnia magna was exposed to the mixture of copper solution and nC60 suspension (100μgL(-1)), LC50 of 48h was lower than that when they were exposed to copper solution alone. This result clearly showed the decrease in NOEC of copper at the presence of nC60. Cu(2+)-ATPase activity was enhanced at the presence of nC60, indicating that copper transport involved with the uptake, distribution and depuration in body was increased. We further conducted experiments on accumulation of copper in D. magna. The observed equilibrium copper concentration in D. magna in the mixture of 100μgL(-1) nC60 and 1μgL(-1) copper solution reached 131μg (kg wet weight)(-1), which was more than twice that in copper solution only: 60μg (kg wet weight)(-1). This result demonstrated that the accumulation of copper in D. magna was significantly enhanced at the presence of even low nC60 concentration. Experiments also showed that copper was quickly adsorbed onto nC60. The absorption of copper onto D. magna was statistically correlated to the absorption of nC60 onto D. magna; this might be caused by nC60 facilitating the transfer of copper into D. magna. The absorption and desorption of copper to nC60 (pH=5.0) reached equilibrium quickly, which may be involved with the co-bioaccumulation and decrease in NOEC of Cu(2+) and nC60.

  8. Ultraviolet-visible absorption spectrum of C60 vapor and determination of the C60 vaporization enthalpy

    NASA Astrophysics Data System (ADS)

    Dai, Sheng; Mac Toth, L.; Del Cul, G. D.; Metcalf, David H.

    1994-09-01

    Ultraviolet-visible absorption spectroscopic studies of C60 vapor were carried out in the temperature range 400 °C-720 °C. The enthalpy of sublimation (180±10 kJ/mol) was obtained through the use of the Clausius-Clapeyron equation.

  9. Silver nanoparticles sensitized C60(Ag@C60) as efficient electrocatalysts for hydrazine oxidation: Implication for hydrogen generation reaction

    NASA Astrophysics Data System (ADS)

    Narwade, Shankar S.; Mulik, Balaji B.; Mali, Shivsharan M.; Sathe, Bhaskar R.

    2017-02-01

    Herein, we report the synthesis of silver nanoparticles (Ag NPs; 10 ± 0.5 nm) sensitized Fullerene (C60; 15 ±2 nm) nanocatalysts (Ag@C60) for the first time showing efficient electroatalytic activity for the oxidation of hydrazine demonstrating activity comparable to that of Pt in acidic, neutral and basic media. The performance is comparable with the best available electrocatalytic system and plays a vital role in the overall hydrogen generation reactions from hydrazine as a one of the fuel cell reaction. The materials are synthesized by a simple and scalable synthetic route involving acid functionalization of C60 followed by chemical reduction of Ag+ ions in ethylene glycol at high temperature. The distributation of Silver nanoparticles (Ag NPs) (morphological information) on C60, bonding, its crystal structure, along with activity towards hydrazine oxidation (electrocatalytic) is studied using TEM, XRD, UV-vis, XPS, FTIR and electrochemical (cyclic voltammetry) studies, respectively. The observed efficient electrocatalytic activity of the as-synthesized electrode is attributed to the co-operative response and associated structural defects due to their oxidative functionalization along with thier cooperative functioning at nanodimensions.

  10. Spin-based diagnostic of nanostructure in copper phthalocyanine-C60 solar cell blends.

    PubMed

    Warner, Marc; Mauthoor, Soumaya; Felton, Solveig; Wu, Wei; Gardener, Jules A; Din, Salahud; Klose, Daniel; Morley, Gavin W; Stoneham, A Marshall; Fisher, Andrew J; Aeppli, Gabriel; Kay, Christopher W M; Heutz, Sandrine

    2012-12-21

    Nanostructure and molecular orientation play a crucial role in determining the functionality of organic thin films. In practical devices, such as organic solar cells consisting of donor-acceptor mixtures, crystallinity is poor and these qualities cannot be readily determined by conventional diffraction techniques, while common microscopy only reveals surface morphology. Using a simple nondestructive technique, namely, continuous-wave electron paramagnetic resonance spectroscopy, which exploits the well-understood angular dependence of the g-factor and hyperfine tensors, we show that in the solar cell blend of C(60) and copper phthalocyanine (CuPc)-for which X-ray diffraction gives no information-the CuPc, and by implication the C(60), molecules form nanoclusters, with the planes of the CuPc molecules oriented perpendicular to the film surface. This information demonstrates that the current nanostructure in CuPc:C(60) solar cells is far from optimal and suggests that their efficiency could be considerably increased by alternative film growth algorithms.

  11. Effect of the structure distortion on the high photocatalytic performance of C60/g-C3N4 composite

    NASA Astrophysics Data System (ADS)

    Ma, Xiaojuan; Li, Xinru; Li, Mengmeng; Ma, Xiangchao; Yu, Lin; Dai, Ying

    2017-08-01

    C60/g-C3N4 composite was reported experimentally to be of high photocatalytic activity in degrading organics. To investigate the underlying mechanism of high photocatalytic performance, the structural and electronic properties of g-C3N4 monolayers with adsorbing and removing fullerene C60 are studied by means of density functional theory calculations. After 25 possible configurations examination, it is found that C60 prefers to stay upon the ;junction nitrogen; with the carbon atom of fullerene being nearest to monolayers. Correspondingly, a type-I band alignment appears. Our results further demonstrate that the adsorption of C60 can lead to an irreversible structure distortion for g-C3N4 from flat to wrinkle, which plays a crucial role in improving photocatalytic performance other than the separation of carriers at interface due to the formation of type-II heterojunctions as previous report. Compared to flat one, the light absorption of wrinkled structure shows augmented, the valence band maximum shifts towards lower position along with a stronger photo-oxidation capability. Interestingly, the results indicate that the energy, light absorption and band edge all have a particular relationship with wrinkle degree. The work presented here can be helpful to understand the mechanism behind the better photocatalytic performance for C60 modified g-C3N4.

  12. Frontier molecular orbitals of a single molecule adsorbed on thin insulating films supported by a metal substrate: electron and hole attachment energies

    NASA Astrophysics Data System (ADS)

    Scivetti, Iván; Persson, Mats

    2017-09-01

    We present calculations of vertical electron and hole attachment energies to the frontier orbitals of a pentacene molecule absorbed on multi-layer sodium chloride films supported by a copper substrate using a simplified density functional theory (DFT) method. The adsorbate and the film are treated fully within DFT, whereas the metal is treated implicitly by a perfect conductor model. We find that the computed energy gap between the highest and lowest unoccupied molecular orbitals—HOMO and LUMO -from the vertical attachment energies increases with the thickness of the insulating film, in agreement with experiments. This increase of the gap can be rationalised in a simple dielectric model with parameters determined from DFT calculations and is found to be dominated by the image interaction with the metal. We find, however, that this simplified model overestimates the downward shift of the energy gap in the limit of an infinitely thick film.

  13. Metal-free phthalocyanine (H2Pc) molecule adsorbed on the Au(111) surface: formation of a wide domain along a single lattice direction

    PubMed Central

    Komeda, Tadahiro; Isshiki, Hironari; Liu, Jie

    2010-01-01

    Using low-temperature scanning tunneling microscopy (STM), we observed the bonding configuration of the metal-free phthalocyanine (H2Pc) molecule adsorbed on the Au(111) surface. A local lattice formation started from a quasi-square lattice aligned to the close-packed directions of the Au(111) surface. Although we expected the lattice alignment to be equally distributed along the three crystallographically equivalent directions, the domain aligned normal to the ridge of the herringbone structure was missing in the STM images. We attribute this effect to the uniaxial contraction of the reconstructed Au(111) surface that can account for the formation of a large lattice domain along a single crystallographical direction. PMID:27877365

  14. David Adler Lectureship Award Talk: Friction and energy dissipation mechanisms in adsorbed molecules and molecularly thin films

    NASA Astrophysics Data System (ADS)

    Krim, Jacqueline

    2015-03-01

    Studies of the fundamental origins of friction have undergone rapid progress in recent years, with the development of new experimental and computational techniques for measuring and simulating friction at atomic length and time scales. The increased interest has sparked a variety of discussions and debates concerning the nature of the atomic-scale and quantum mechanisms that dominate the dissipative process by which mechanical energy is transformed into heat. Measurements of the sliding friction of physisorbed monolayers and bilayers can provide information on the relative contributions of these various dissipative mechanisms. Adsorbed films, whether intentionally applied or present as trace levels of physisorbed contaminants, moreover are ubiquitous at virtually all surfaces. As such, they impact a wide range of applications whose progress depends on precise control and/or knowledge of surface diffusion processes. Examples include nanoscale assembly, directed transport of Brownian particles, material flow through restricted geometries such as graphene membranes and molecular sieves, passivation and edge effects in carbon-based lubricants, and the stability of granular materials associated with frictional and frictionless contacts. Work supported by NSFDMR1310456.

  15. (CH3Br⋯NH3)@C60: The effect of nanoconfinement on halogen bonding

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    Halogen bonds resemble hydrogen bonds in many aspects. How do the properties of halogen bonds change when confined to nanoregion? In order to explore this, we have encapsulated a halogen bonded complex, CH3Br⋯NH3 inside C60 fullerene and studied their properties using density functional theory and quantum theory of atoms in molecule. Our findings show that the geometry of CH3Br⋯NH3 complex is appreciably bent inside C60, interaction becomes covalent with larger interaction energy, unlike free CH3Br⋯NH3 complex, which is linear with closed shell interaction. Thus, the halogen bonded complexes show quite different properties at nanoscale.

  16. Crystallinity of the epitaxial heterojunction of C60 on single crystal pentacene

    NASA Astrophysics Data System (ADS)

    Tsuruta, Ryohei; Mizuno, Yuta; Hosokai, Takuya; Koganezawa, Tomoyuki; Ishii, Hisao; Nakayama, Yasuo

    2017-06-01

    The structure of pn heterojunctions is an important subject in the field of organic semiconductor devices. In this work, the crystallinity of an epitaxial pn heterojunction of C60 on single crystal pentacene is investigated by non-contact mode atomic force microscopy and high-resolution grazing incidence x-ray diffraction. Analysis shows that the C60 molecules assemble into grains consisting of single crystallites on the pentacene single crystal surface. The in-plane mean crystallite size exceeds 0.1 μm, which is at least five time larger than the size of crystallites deposited onto polycrystalline pentacene thin films grown on SiO2. The results indicate that improvement in the crystal quality of the underlying molecular substrate leads to drastic promotion of the crystallinity at the organic semiconductor heterojunction.

  17. Polarons in endohedral Li+@C60- dimers and in 1D and 2D crystals

    NASA Astrophysics Data System (ADS)

    Kawazoe, Yoshiyuki; Belosludov, Vladimir R.; Zhdanov, Ravil K.; Belosludov, Rodion V.

    2017-10-01

    The electron charge distribution and polaron formation on the carbon sites of dimer clusters Li+@C60- and of 1D or 2D Li+@C60- periodic systems are studied with the use of the generalized Su-Schrieffer-Heeger model with respect to the intermolecular and intramolecular degrees of freedom. The charge distributions over the molecular surface and Jahn-Teller bond distortions of carbon atoms are calculated using the self-consistent iterative methods. Polarons formed in periodic 1D and 2D systems (chains and planar layers) as well as in dimer cluster system are examined. In the periodic systems polaron formation may be described by the cooperative Jahn-Teller effect. Orientation of the polarons on the molecule surface depends on the doping of the system, moreover, electron doping changes the energy levels in the system.

  18. 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.

  19. Monolayer of Hydrazine Facilitates the Direct Covalent Attachment of C60 Fullerene to a Silicon Surface.

    PubMed

    Gao, Fei; Teplyakov, Andrew V

    2017-02-13

    The development of oxygen-free organic-inorganic interfaces has led to new schemes for the functionalization of silicon surfaces with nitrogen-based chemical groups. However, building layers of large structures directly on this functionalized surface has remained elusive. This work confirms the path to form a stable interface between silicon and buckminsterfullerene C60 based on covalent chemical bonds. The starting point for this modification is the hydrazine-reacted Si(111) surface with the diamine functionality, which is further reacted directly with the C60 molecules. The chemistry of this process is confirmed spectroscopically and microscopically and can be used to form organic-inorganic interfaces separated by a single layer of nitrogen.

  20. Microscopic dynamics of an amorphous C60 x /C70(1 - x) fullerene mixture

    NASA Astrophysics Data System (ADS)

    Khusnutdinoff, R. M.; Mokshin, A. V.; Takhaviev, I. D.

    2015-02-01

    This paper presents the results of investigation of the propagation mechanism of collective excitations in amorphous C60 x /C70(1 - x) fullerene mixtures (with equimolar concentration x = 0.50), which were obtained using molecular dynamics simulation. The critical glass-transition temperature of the system T c = 1548 K was determined from the change in the behavior of the Wendt-Abraham parameter. Spectral densities of the time correlation functions of the longitudinal and transverse currents for a wide region of wave numbers at temperatures below the glass-transition temperature were calculated. It was found that the dynamics of density fluctuations in amorphous C60 x /C70(1 - x) fullerene mixtures is characterized by two dispersion acoustic-like branches of the longitudinal and transverse polarizations. The influence of poly-dispersity and form factor of the molecule of the mixture component on the microscopic dynamics of the density fluctuation in multicomponent systems was established.

  1. On the widths of Stokes lines in Raman scattering from molecules adsorbed at metal surfaces and in molecular conduction junctions

    NASA Astrophysics Data System (ADS)

    Gao, Yi; Galperin, Michael; Nitzan, Abraham

    2016-06-01

    Within a generic model we analyze the Stokes linewidth in surface enhanced Raman scattering (SERS) from molecules embedded as bridges in molecular junctions. We identify four main contributions to the off-resonant Stokes signal and show that under zero voltage bias (a situation pertaining also to standard SERS experiments) and at low bias junctions only one of these contributions is pronounced. The linewidth of this component is determined by the molecular vibrational relaxation rate, which is dominated by interactions with the essentially bosonic thermal environment when the relevant molecular electronic energy is far from the metal(s) Fermi energy(ies). It increases when the molecular electronic level is close to the metal Fermi level so that an additional vibrational relaxation channel due to electron-hole (eh) exciton in the molecule opens. Other contributions to the Raman signal, of considerably broader linewidths, can become important at larger junction bias.

  2. Cu-C60 nanocomposite with suppressed recrystallization

    NASA Astrophysics Data System (ADS)

    Medvedev, V. V.; Popov, M. Y.; Mavrin, B. N.; Denisov, V. N.; Kirichenko, A.; Tat'yanin, E. V.; Ivanov, L. A.; Aksenenkov, V. V.; Perfilov, S. A.; Lomakin, R.; Blank, V. D.

    2011-10-01

    Cu matrix composite reinforced with fullerene (C60) was fabricated by ball milling, followed by hot pressing techniques. The microstructure characteristics of the composite were investigated at different temperatures. The mechanical properties of the composite were measured at room temperature. The experimental result showed that the composite temperature recrystallization is impeded by carbon modification of copper grain boundaries. Furthermore, the nanocomposite possesses a very high hardness (up to 4 GPa).

  3. Fullerenes C60 and C70 in flames

    NASA Astrophysics Data System (ADS)

    Howard, Jack B.; McKinnon, J. Thomas; Makarovsky, Yakov; Lafleur, Arthur L.; Johnson, M. Elaine

    1991-07-01

    THE fullerenes C60 and C70 were first identified1 in carbon vapour produced by laser irradiation of graphite, and have recently been produced in macroscopic quantities2-5 by vaporization of graphite with resistive heating. It has also been suggested6-9 that fullerenes might be formed in sooting flames, and indeed all-carbon ions with mass/charge ratios suggestive of fullerenes have been detected in flames10-12. These species were assumed to have the cage structures of fullerenes, but the mass spectroscopic evidence could not establish this conclusively. We have now collected samples of condensible compounds and soot from hydrocarbon combustion under a range of conditions, and analysed these using conventional techniques in an effort to detect fullerenes. Spectroscopic studies reveal the presence of C60 and C70 in yields and ratios that depend on temperature, pressure, carbon/oxygen ratio and residence time in the flame. Control of these conditions allows optimal yields of 3 g of fullerenes per kilogram of fuel carbon burned, and variation of the C70/C60 ratio over the range 0.26-5.7.

  4. Enhancing superconductivity in A3C60 fullerides

    NASA Astrophysics Data System (ADS)

    Kim, Minjae; Nomura, Yusuke; Ferrero, Michel; Seth, Priyanka; Parcollet, Olivier; Georges, Antoine

    2016-10-01

    Motivated by the recent experimental report of a possible light-induced superconductivity in K3C60 at high temperature [Mitrano et al., Nature 530, 451 (2016), 10.1038/nature16522], we investigate theoretical mechanisms for enhanced superconductivity in A3C60 fullerenes. We find that an "interaction imbalance" corresponding to a smaller value of the Coulomb matrix element for two of the molecular orbitals in comparison to the third one, efficiently enhances superconductivity. Furthermore, we perform first-principle calculations of the changes in the electronic structure and in the screened Coulomb matrix elements of K3C60 , brought in by the deformation associated with the pumped T1 u intramolecular mode. We find that an interaction imbalance is indeed induced, with a favorable sign and magnitude for superconductivity enhancement. The physical mechanism responsible for this enhancement consists of a stabilization of the intramolecular states containing a singlet pair, while preserving the orbital fluctuations allowing for a coherent interorbital delocalization of the pair. Other perturbations have also been considered and found to be detrimental to superconductivity. The light-induced deformation and ensuing interaction imbalance is shown to bring superconductivity further into the strong-coupling regime.

  5. Nanobionics of Pharmacologically Active Derivatives of Fullerene C60

    NASA Astrophysics Data System (ADS)

    Kotelnikova, R. A.; Bogdanov, G. N.; Frog, E. C.; Kotelnikov, A. I.; Shtolko, V. N.; Romanova, V. S.; Andreev, S. M.; Kushch, A. A.; Fedorova, N. E.; Medzhidova, A. A.; Miller, G. G.

    2003-12-01

    The physical-chemical mechanisms of pharmacologic functioning of amino acid derivatives of fullerene C60 (ADF) have been studied. ADF were shown to penetrate through the lipid bilayer of liposomes without destruction of membrane integrity. ADF are able to carry bivalent metal ions through phospholipid bilayer owing to the formation of complexes. It was shown that stereoisomers of ADF selectively penetrate into phospholipid membranes. In contrast to D-isomers, L-isomers penetrate through the phosphatidylcholine membrane into liposome interior. Stereo-specific effect of ADF enantiomers was also observed in reaction of peroxidation of lipids. Besides that, ADF bring about a substantial increase in the catalytic activity of monoaminoxidases A and B. The directed intraprotein electron transfer was studied by creating a donor-acceptor pair in a water solution in the presence of ADF. To realize the intraprotein electron transfer, the model system was produced on the base of apomyoglobin by incorporating ADF (electron acceptor) into the heme pocket of protein instead of removed heme. It was established that the fullerene C60 and its derivatives did not produce specific anti-C60 antibodies, both IgG and IgE classes, while ADF themselves are efficient adjuvants, i.e. they increased the antibody response to poor antigens. Some ADF were found to inhibit the human immunodeficiency virus and human cytomegalovirus infection.

  6. 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.

  7. On the nature of electron correlation in C60

    NASA Astrophysics Data System (ADS)

    Stück, David; Baker, Thomas A.; Zimmerman, Paul; Kurlancheek, Westin; Head-Gordon, Martin

    2011-11-01

    The ground state restricted Hartree Fock (RHF) wave function of C60 is found to be unstable with respect to spin symmetry breaking, and further minimization leads to a significantly spin contaminated unrestricted Hartree Fock (UHF) solution ( = 7.5, 9.6 for singlet and triplet, respectively). The nature of the symmetry breaking in {C_{60}} relative to the radicaloid fullerene, {C_{36}}, is assessed by energy lowering of the UHF solution, , and the unpaired electron number. We conclude that the high value of each of these measures in {C_{60}} is not attributable to strong correlation behavior as is the case for {C_{36}}. Instead, their origin is from the collective effect of relatively weak, global correlations present in the π space of both fullerenes. Second order perturbation (MP2) calculations of the singlet triplet gap are significantly more accurate with RHF orbitals than UHF orbitals, while orbital optimized opposite spin second order correlation (O2) performs even better.

  8. High-resolution 13C NMR studies of high-pressure-polymerized C60: Evidence for the [2+2] cycloaddition structure in the rhombohedral two-dimensional C60 polymer

    NASA Astrophysics Data System (ADS)

    Goze, C.; Rachdi, F.; Hajji, L.; Núñez-Regueiro, M.; Marques, L.; Hodeau, J.-L.; Mehring, M.

    1996-08-01

    We report on 13C NMR measurements of a rhombohedral two-dimensional polymer of C60 obtained under high pressure. By spinning the sample up to 12 kHz, we were able to identify six resonances at 149.1, 147.9, 145.2, 139.6, 134.8, and 73.5 ppm. The static distortion of the C60 molecules induced by the transformation under pressure must be at the origin of the observed inequivalent carbons in the polymer. The 13C NMR line shape simulation of the obtained spectrum is compatible with the suggested polymeric structures where the C60 molecules are connected by [2+2] cycloadditions.

  9. Orbital tomography: Molecular band maps, momentum maps and the imaging of real space orbitals of adsorbed molecules.

    PubMed

    Offenbacher, Hannes; Lüftner, Daniel; Ules, Thomas; Reinisch, Eva Maria; Koller, Georg; Puschnig, Peter; Ramsey, Michael G

    2015-10-01

    The frontier orbitals of molecules are the prime determinants of their chemical, optical and electronic properties. Arguably, the most direct method of addressing the (filled) frontier orbitals is ultra-violet photoemission spectroscopy (UPS). Although UPS is a mature technique from the early 1970s on, the angular distribution of the photoemitted electrons was thought to be too complex to be analysed quantitatively. Recently angle resolved UPS (ARUPS) work on conjugated molecules both, in ordered thick films and chemisorbed monolayers, has shown that the angular (momentum) distribution of the photocurrent from orbital emissions can be simply understood. The approach, based on the assumption of a plane wave final state is becoming known as orbital tomography. Here we will demonstrate, with selected examples of pentacene (5A) and sexiphenyl (6P), the potential of orbital tomography. First it will be shown how the full angular distribution of the photocurrent (momentum map) from a specific orbital is related to the real space orbital by a Fourier transform. Examples of the reconstruction of 5A orbitals will be given and the procedure for recovering the lost phase information will be outlined. We then move to examples of sexiphenyl where we interrogate the original band maps of thick sexiphenyl in the light of our understanding of orbital tomography that has developed since then. With comparison to theoretical simulations of the molecular band maps, the molecular conformation and orientation will be concluded. New results for the sexiphenyl monolayer on Al(1 1 0) will then be presented. From the band maps it will be concluded that the molecule is planarised and adopts a tilted geometry. Finally the momentum maps down to HOMO-11 will be analysed and real space orbitals reconstructed.

  10. Photophysics of pristine and C60-doped disubstituted polyacetylene

    NASA Astrophysics Data System (ADS)

    Gontia, I. I.; Vardeny, Z. V.; Masuda, T.; Yoshino, K.

    2002-08-01

    Using a variety of steady-state spectroscopies we studied the long-lived photoexcitations and electronic excited states of poly disubstituted acetylene (PDPA-nBu), the backbone structure of which is a disubstituted trans-polyacetylene, as well as PDPA-nBu/C60 blends. The cw spectroscopies include absorption, photoluminescence (PL), photoinduced absorption (PA), and PA-detected magnetic resonance (PADMR). Although PDPA-nBu is a degenerate ground-state polymer, nevertheless, and in contrast to trans-polyacetylene, we found that it has a strong PL band with quantum efficiency larger than 60%. From polarized PL studies on stretched oriented films we conclude that the PL emission originates from intrachain excitons rather than the polymer side groups. This shows that the lowest-lying exciton in PDPA-nBu is a Bu state rather than an Ag state, in contrast to the order of the lowest-lying excitonic states in trans-polyacetylene. The polarized absorption in PDPA-nBu contains three distinctly different bands with different polarization properties, which are interpreted according to the model of Shukla and Mazumdar. The PA spectra of pristine and photo-oxidized PDPA-nBu films show neutral and charged solitons as well as polaron excitations, whereas the long-lived photoexcitations in PDPA-nBu in solution are mainly polarons. This may be due to destabilization of the soliton-antisoliton pairs in the polymer chains in solution caused by short conjugation length. From the PA and PADMR spectroscopies of PDPA-nBu/C60 blends we conclude that a photoinduced charge-transfer reaction takes place, again in contrast to blends of other nonluminescent polymers. Interestingly the PA spectrum of PDPA-nBu/C60 blends shows both charged polarons and charged solitons that are correlated with the PA band of C-60. We found that the ratio between charged solitons and polaron excitations depends on the C60 concentration in the blend, the film morphology, and temperature. It is shown that the

  11. [Coupled Cytotoxicity of C60 Nano-Crystal Particle with Cu2+ to the Mouse Peritoneal Macrophage RAW 264.7].

    PubMed

    Yu, Ye; Bian, Wei-lin; Zhang, Hui-min; Zhang, Bo; He, Yi-liang

    2015-07-01

    This work evaluated the cytotoxicity effect of nC60 nano-crystal particle associated with Cu2+ by using mouse peritoneal microphage RAW264. 7 as the test cell line. The results showed that when exposed to nC60 of 6. 6 mg . L-1 and 9. 9 mg . L-1 for 24h, the cell viability decreased 45% and 70% , respectively, and had obvious time-response and dose-response. It was found that Cu2, could reduce the toxicity of nC60 on RAW 264. 7. The cell viability reduced to 25% when exposed to 6. 6 mg . L-1 nC60 with 2 mg . L-1 Cu2+, and reduced to 15% when exposed to 9. 9 mg . L-1 nC60 with 5 mg . L-1 Cu2+. The nC60 could adsorb Cu2+ and the adsorption isotherm was fitted to the Langmuir adsorptiqn isotherm. The adsprption of Cu2+ on the surface of nC60 may decrease the cytotoxicity nC60 on RAW 264.7.

  12. High resolution13C NMR studies of one- and two-dimensional polymerized C60 under high pressure

    NASA Astrophysics Data System (ADS)

    Rachdi, F.; Goze, C.; Hajji, L.; Nún˜Ez-Regueiro, M.; Marques, L.; Hodeau, J.-L.; Mehring, M.

    1997-11-01

    We report on13C NMR measurements of orthorhombic one-dimensional and rhombohedral two-dimensional polymers of C60 obtained under high pressure. The obtained13C MAS NMR spectrum of the orthorhombic polymer shows two resonances at 146 ppm and 73.5 ppm, and the one of the rhombohedral polymer presents six isotropic lines at 149.1, 147.9, 145.2, 139.6, 134.8 and 73.5 ppm. The static distortion of the C60 molecules induced by the transformation under pressure must be at the origin of the observed inequivalent carbons in both systems. The13C NMR lineshape simulation of the obtained spectra are compatible with the suggested polymeric structures where the C60 molecules are connected by [2 + 2] cycloadditions.

  13. Energy distributions of atomic and molecular ions sputtered by C 60+ projectiles

    NASA Astrophysics Data System (ADS)

    Delcorte, A.; Poleunis, C.; Bertrand, P.

    2006-07-01

    In the process of investigating the interaction of fullerene projectiles with adsorbed organic layers, we measured the kinetic energy distributions (KEDs) of fragment and parent ions sputtered from an overlayer of polystyrene (PS) oligomers cast on silver under 15 keV C 60+ bombardment. These measurements have been conducted using our TRIFT™ spectrometer, recently equipped with the C 60+ source developed by Ionoptika, Ltd. For atomic ions, the intensity corresponding to the high energy tail decreases in the following order: C +( E-0.4) > H +( E-1.5) > Ag +( E-3.5). In particular, the distribution of Ag + is not broader than those of Ag 2+ and Ag 3+ clusters, in sharp contrast with 15 keV Ga + bombardment. On the other hand, molecular ions (fragments and parent-like species) exhibit a significantly wider distribution using C 60+ instead of Ga + as primary ions. For instance, the KED of Ag-cationized PS oligomers resembles that of Ag + and Ag n+ clusters. A specific feature of fullerene projectiles is that they induce the direct desorption of positively charged oligomers, without the need of a cationizing metal atom. The energy spectrum of these PS + ions is significantly narrower then that of Ag-cationized oligomers. For characteristic fragments of PS, such as C 7H 7+ and C 15H 13+ and polycyclic fragments, such as C 9H 7+ and C 14H 10+, the high energy decay is steep ( E-4 - E-8). In addition, reorganized ions generally show more pronounced high energy tails than characteristic ions, similar to the case of monoatomic ion bombardment. This observation is consistent with the higher excitation energy needed for their formation. Finally, the fraction of hydrocarbon ions formed in the gas phase via unimolecular dissociation of larger species is slightly larger with gallium than with fullerene projectiles.

  14. Cross-linking of C60 films with 1,8-diaminooctane and further decoration with silver nanoparticles.

    PubMed

    Meza-Laguna, V; Basiuk, E V; Alvarez-Zauco, E; Acosta-Najarro, D; Basiuk, V A

    2007-10-01

    We applied the direct solvent-free functionalization of fullerene C60 with aliphatic bifunctional amine, 1,8-diaminooctane, to prepare chemically cross-linked C60 thin films capable of binding silver nanoparticles. The gas-phase diamine treatment of C60 reduced dramatically the fullerene solubility in toluene, indicating the transformation of pristine C60 into a different solid phase with cross-linked fullerene molecules. Compared to the spectra of pristine C60 film and powder samples, Fourier-transform infrared, UV-Visible, Raman, and 13C nucleic magnetic resonance spectra of the functionalization products exhibited new features, which point to a breaking of C60 ideal structure during the formation of new covalent bonds and to the appearance of sp3 hibridization. The covalent functionalization with 1,8-diaminooctane allowed for a stable and homogeneous deposition of silver nanoparticles of ca. 5-nm diameter onto the functionalized films through the coordination bonding between metal atoms and nitrogen donor atoms of the fullerene derivatives. The proposed mechanism of Ag nanoparticle binding was supported by density functional theory calculations using the hybrid BLYP functional in conjunction with the double numerical basis set DND.

  15. Excited-state potential-energy surfaces of metal-adsorbed organic molecules from linear expansion Δ-self-consistent field density-functional theory (ΔSCF-DFT)

    NASA Astrophysics Data System (ADS)

    Maurer, Reinhard J.; Reuter, Karsten

    2013-07-01

    Accurate and efficient simulation of excited state properties is an important and much aspired cornerstone in the study of adsorbate dynamics on metal surfaces. To this end, the recently proposed linear expansion Δ-self-consistent field method by Gavnholt et al. [Phys. Rev. B 78, 075441 (2008)], 10.1103/PhysRevB.78.075441 presents an efficient alternative to time consuming quasi-particle calculations. In this method, the standard Kohn-Sham equations of density-functional theory are solved with the constraint of a non-equilibrium occupation in a region of Hilbert-space resembling gas-phase orbitals of the adsorbate. In this work, we discuss the applicability of this method for the excited-state dynamics of metal-surface mounted organic adsorbates, specifically in the context of molecular switching. We present necessary advancements to allow for a consistent quality description of excited-state potential-energy surfaces (PESs), and illustrate the concept with the application to Azobenzene adsorbed on Ag(111) and Au(111) surfaces. We find that the explicit inclusion of substrate electronic states modifies the topologies of intra-molecular excited-state PESs of the molecule due to image charge and hybridization effects. While the molecule in gas phase shows a clear energetic separation of resonances that induce isomerization and backreaction, the surface-adsorbed molecule does not. The concomitant possibly simultaneous induction of both processes would lead to a significantly reduced switching efficiency of such a mechanism.

  16. Fabrication of C 60 nanostructures by selective growth on GaSe/MoS 2 and InSe/MoS 2 heterostructure substrates

    NASA Astrophysics Data System (ADS)

    Ueno, Keiji; Sasaki, Kentaro; Nakahara, Tomonori; Koma, Atsushi

    1998-06-01

    C 60 molecules were deposited on a submonolayer InSe film which was grown on a MoS 2 substrate. In the previous experiment on the growth of a C 60 thin film on a GaSe/MoS 2 heterostructure, C 60 grew only on exposed MoS 2 regions and never nucleated on GaSe domains at substrate temperature above 180°C. In the present case, however, C 60 molecules grow only on InSe domains and do not nucleate on the exposed MoS 2 when the substrate temperature is higher than 80°C. Using this method, C 60 domains whose dimension is smaller than 100 nm could be fabricated on each InSe domain. The selectivity of the C 60 growth is supposed to originate not from the surface morphology of those heterostructures, but from the difference in adsorption energy and surface diffusion energy of C 60 molecules on the surfaces of three different layered materials and a C 60 film.

  17. 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

    2016-08-02

    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%.

  18. Intensity-resolved IR multiple photon ionization and fragmentation of C60.

    PubMed

    Bakker, Joost M; Lapoutre, Vivike J F; Redlich, Britta; Oomens, Jos; Sartakov, Boris G; Fielicke, André; von Helden, Gert; Meijer, Gerard; van der Meer, Alexander F G

    2010-02-21

    The sequential absorption of multiple infrared (IR) photons by isolated gas-phase species can lead to their dissociation and/or ionization. Using the newly constructed "Free-Electron Laser for IntraCavity Experiments" (FELICE) beam line at the FELIX facility, neutral C(60) molecules have been exposed to an extremely high number (approximately 10(23)) of photons/cm(2) for a total time duration of up to 5 micros. At wavelengths around 20 microm, resonant with allowed IR transitions of C(60), ionization and extensive fragmentation of the fullerenes are observed. The resulting photofragment distributions are attributed to absorption in fragmentation products formed once C(60) is excited to internal energies at which fragmentation or ionization takes place within the duration of the laser pulse. The high IR intensities available combined with the large interaction volume permit spatially resolved detection of the ions inside the laser beam, thereby disentangling the contributions from different IR intensities. The use of spatial imaging reveals intensity dependent mass distributions that are substantially narrower than what has been observed previously, indicating rather narrow energy distributions. A simple rate-equation modeling of the excitation process supports the experimental observations.

  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.

  20. Energy level alignment at C60/DTDCTB/PEDOT:PSS interfaces in organic photovoltaics

    NASA Astrophysics Data System (ADS)

    Yoo, Jisu; Jung, Kwanwook; Jeong, Junkyeong; Hyun, Gyeongho; Lee, Hyunbok; Yi, Yeonjin

    2017-04-01

    The electronic structure of a narrow band gap small molecule ditolylaminothienyl-benzothiadiazole-dicyanovinylene (DTDCTB), possessing a donor-acceptor-acceptor configuration, was investigated with regard to its application as an efficient donor material in organic photovoltaics (OPVs). The interfacial orbital alignment of C60/DTDCTB/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) was determined using in situ ultraviolet photoelectron and inverse photoelectron spectroscopic methods. The ionization energy and electron affinity values of DTDCTB were measured to be 5.27 eV and 3.65 eV, respectively, and thus a very small transport gap of 1.62 eV was evaluated. Large band bending of DTDCTB on PEDOT:PSS was observed, resulting in a low hole extraction barrier. Additionally, the photovoltaic gap between the highest occupied molecular orbital level of the DTDCTB donor and the lowest unoccupied molecular orbital level of the C60 acceptor was estimated to be 1.30 eV, which is known to be the theoretical maximum open-circuit voltage in OPVs employing the C60/DTDCTB active layer. The unique electronic structures of DTDCTB contributed toward the recently reported excellent power conversion efficiencies of OPVs containing a DTDCTB donor material.

  1. Functionalization of silicon dioxide surface with 3-aminopropyltrimethoxysilane for fullerene C60 immobilization.

    PubMed

    Delafosse, Grégory; Patrone, Lionel; Goguenheim, Didier

    2011-10-01

    Formation of self-assembled monolayers (SAM) of 3-aminopropyltrimethoxysilane (APTMS), chemically bonded to silicon dioxide surface, using a new solvent free process, has been studied by contact angle measurements, ellipsometry, ATR-FTIR spectroscopy and AFM imaging. The possibility of using as-obtained APTMS SAMs for anchoring functional molecular moieties is then studied with fullerene C60. In a first part we have analyzed the grafting kinetics of APTMS SAMs in order to control the formation of a single monolayer. Results show that about four hours are needed to obtain a complete APTMS single monolayer. In parallel, the ordering kinetics of the SAM has been monitored by ATR-FTIR spectroscopy, showing that the monolayer reaches its final order before grafting. We show that those APTMS SAMs can be used to graft C60 molecules deposited from a solution and forming about one monolayer anchored on amine terminal moieties. Such results could help paving the way to the preparation of hybrid C60-based molecular devices on silicon through a bottom-up approach.

  2. Hydrodynamic model of the collective electron resonances in C60 fullerene

    NASA Astrophysics Data System (ADS)

    Gildenburtg, V. B.; Pavlichenko, I. A.

    2017-08-01

    The polarization-response spectrum of the fullerene C60 modeled as a homogeneous spherical plasma shell is calculated in the framework of the hydrodynamic approach, allowing for the spatial dispersion caused by the Fermi-distributed valence electrons. The dipole eigenoscillation spectrum of the shell is found to contain a series of plasmons distinguished by the frequency and the radial structure. The first two of them (whose structures for C60 are the subject of discussion up to now) pass to the lower and higher surface plasmons of the plasma shell if its thickness is much larger than the Tomas-Fermi length. However, under parameter values corresponding to the C60 molecule, when these lengths are of the same order, both these plasmons (providing the main contribution to the fullerene absorption spectrum) are found to be actually volume ones in their spatial structure, and the frequency of the higher of them becomes larger than the plasma frequency (as with all the higher volume plasmons). The resonance curve of the fullerene absorption cross-section calculated on the basis of the developed model with allowance for the surface losses caused by the reflection of electrons at the shell boundaries agrees well with the experimental data.

  3. Ferromagnetism in C60 polymers: pure carbon or contamination with metallic impurities?

    PubMed

    Talyzin, A V; Dzwilewski, A

    2007-01-01

    A review of ferromagnetism in C60 polymeric materials synthesized by high pressure high temperature (HPHT) treatment is presented. Analysis of published data proves that the reported ferromagnetism cannot be assigned to polymeric structure in either perfect or defect states. Most recent experimental studies have not confirmed previously reported levels of magnetization in polymeric samples while it appears that ferromagnetism of "magnetic carbon" is preserved above the depolymerization point of any C60 polymer. Identical ferromagnetic properties in some samples of fullerene polymer and graphite like hard carbon phase also show that the effect is most likely not connected to fullerenes at all. Most of the data published previously as an evidence of ferromagnetism in C60 polymers synthesized at HPHT conditions can be explained by contamination with magnetic impurities. Formation of iron carbide (Fe3C) due to reaction of metallic iron with fullerene molecules allows to explain observed Curie temperature of approximately 500 K and levels of magnetization reported for "magnetic carbon".

  4. Electronic correlations and magnetic ordering in CsC60

    NASA Astrophysics Data System (ADS)

    Thier, K.-F.; Mehring, M.; Rachdi, F.

    1998-08-01

    We investigate the spin arrangement in the magnetically ordered orthorhombic phase of CsC60 by a comparison of 133Cs NMR data and simulations of a 3D ordered anisotropic antiferromagnet. Consistent results are obtained for two different magnetic ordering vectors. The agreement between simulation and experiment can be further improved by including a substantial amount of magnetic disorder. In addition, the metastable low temperature cubic phase is investigated using 13C NMR. We find a strongly correlated metallic system that transforms to the semiconducting dimer phase at T=140 K.

  5. Organic field effect transistor composed by fullerene C60 and heterojunctions

    NASA Astrophysics Data System (ADS)

    Vasconcelos, Railson C.; Aleixo, Vicente F. P.; Del Nero, Jordan

    2017-02-01

    We present a study of the complex electronic behavior of a fullerene (C60) molecule attached to six leads (heterojunctions), which works as a three-dimension rectifier. In addition, we confirmed that the fullerene works not only as an electron donor, but also as barrier and transport channel to electrons through the molecule. Moreover, when the phenylpropanodinilla (PPP) lead is orthogonally subjected to bias voltage, the charge distribution and the current displays regions of saturation and resonance similar to semiconductor devices. In order to understand the electronic transport in the molecule, we applied non-equilibrium green function (NEGF) method and performed Fowler-Nordheim (FN) and Millikan-Lauritsen (ML) analyses. The ML curves proved to be sufficient to describe the FN characteristics. In this work, we report the theoretical design for electronic transport of a 3D device (6-terminal).

  6. Modeling adsorption: Investigating adsorbate and adsorbent properties

    NASA Astrophysics Data System (ADS)

    Webster, Charles Edwin

    1999-12-01

    Surface catalyzed reactions play a major role in current chemical production technology. Currently, 90% of all chemicals are produced by heterogeneously catalyzed reactions. Most of these catalyzed reactions involve adsorption, concentrating the substrate(s) (the adsorbate) on the surface of the solid (the adsorbent). Pore volumes, accessible surface areas, and the thermodynamics of adsorption are essential in the understanding of solid surface characteristics fundamental to catalyst and adsorbent screening and selection. Molecular properties such as molecular volumes and projected molecular areas are needed in order to convert moles adsorbed to surface volumes and areas. Generally, these molecular properties have been estimated from bulk properties, but many assumptions are required. As a result, different literature values are employed for these essential molecular properties. Calculated molar volumes and excluded molecular areas are determined and tabulated for a variety of molecules. Molecular dimensions of molecules are important in the understanding of molecular exclusion as well as size and shape selectivity, diffusion, and adsorbent selection. Molecular dimensions can also be used in the determination of the effective catalytic pore size of a catalyst. Adsorption isotherms, on zeolites, (crystalline mineral oxides) and amorphous solids, can be analyzed with the Multiple Equilibrium Analysis (MEA) description of adsorption. The MEA produces equilibrium constants (Ki), capacities (ni), and thermodynamic parameters (enthalpies, ΔHi, and entropies, ΔSi) of adsorption for each process. Pore volumes and accessible surface areas are calculated from the process capacities. Adsorption isotherms can also be predicted for existing and new adsorbate-adsorbent systems with the MEA. The results show that MEA has the potential of becoming a standard characterization method for microporous solids that will lead to an increased understanding of their behavior in gas

  7. A theoretical study of the XP and NEXAFS spectra of alanine: gas phase molecule, crystal, and adsorbate at the ZnO(10 ̅10) surface.

    PubMed

    Gao, You Kun; Traeger, Franziska; Kotsis, Konstantinos; Staemmler, Volker

    2011-06-14

    The adsorption of alanine on the mixed-terminated ZnO(10 ̅10) surface is studied by means of quantum-chemical ab initio calculations. Using a finite cluster model and the adsorption geometry as obtained both by periodic CPMD and embedded cluster calculations, the C1s, N1s and O1s X-ray photoelectron spectra (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectra are calculated for single alanine molecules on ZnO(10 ̅10). These spectra are compared with the spectra calculated for alanine in the gas phase and in its crystalline form and with experimental XPS and NEXAFS data for the isolated alanine molecule and for alanine adsorbed on ZnO(10 ̅10) at multilayer and monolayer coverage. The excellent agreement between the experimental and calculated XP and NEXAFS spectra confirms the calculated adsorption geometry: A single alanine molecule is bound to ZnO(10 ̅10) in a dissociated bidentate form with the two O atoms of the acid group bound to two Zn atoms of the surface and the proton transferred to one O atom of the surface. Other possible structures, such as adsorption of alanine in one of its neutral or zwitterionic forms in which the proton of the -COOH group remains at this group or is transferred to the amino group, can be excluded since they would give rise to quite different XP spectra. In the multilayer coverage regime, on the other hand, alanine is in its crystalline form as is also shown by the analysis of the XP spectra.

  8. Mechanical oscillatory behavior of a C60 fullerene tunneling through open carbon nanocones

    NASA Astrophysics Data System (ADS)

    Sadeghi, F.; Ansari, R.

    2017-07-01

    This paper deals with the mechanical oscillatory behavior of a C60 fullerene inside open carbon nanocones (CNCs). The fullerene molecule is assumed to enter the nanocone through its small end or wide end. Following our previously published study, semi-analytical expressions for the evaluation of vdW interactions are presented which facilitate obtaining a formula for oscillation frequency. The equation of motion is numerically solved to attain the time histories of separation distance and velocity of the fullerene molecule. Based on the conservation of the mechanical energy law, a new semi-analytical formula is also derived to accurately evaluate the oscillation frequency of the system. With respect to the present formulation, a detailed parametric study is conducted to gain an insight into the effects of both geometrical parameters (small-end radius, wide-end radius and vertex angle of nanocone) and initial conditions (initial separation distance and initial velocity) on the oscillatory behavior of C60 fullerene-open CNC oscillators. For given geometrical parameters and initial conditions, it is shown that higher oscillation frequencies can be achieved when the fullerene molecule enters the open nanocone through its small end.

  9. Complex interplay between formation routes and natural organic matter modification controls capabilities of C60 nanoparticles (nC60) to accumulate organic contaminants.

    PubMed

    Hou, Lei; Fortner, John D; Wang, Ximeng; Zhang, Chengdong; Wang, Lilin; Chen, Wei

    2017-01-01

    Accumulation of organic contaminants on fullerene nanoparticles (nC60) may significantly affect the risks of C60 in the environment. The objective of this study was to further understand how the interplay of nC60 formation routes and humic acid modification affects contaminant adsorption of nC60. Specifically, adsorption of 1,2,4,5-tetrachlorobenzene (a model nonionic, hydrophobic organic contaminant) on nC60 was greatly affected by nC60 formation route - the formation route significantly affected the aggregation properties of nC60, thus affecting the available surface area and the extent of adsorption via the pore-filling mechanism. Depending on whether nC60 was formed via the "top-down" route (i.e., sonicating C60 powder in aqueous solution) or "bottom-up" route (i.e., phase transfer from an organic solvent) and the type of solvent involved (toluene versus tetrahydrofuran), modification of nC60 with Suwannee River humic acid (SRHA) could either enhance or inhibit the adsorption affinity of nC60. The net effect depended on the specific way in which SRHA interacted with C60 monomers and/or C60 aggregates of different sizes and morphology, which determined the relative importance of enhanced adsorption from SRHA modification via preventing C60 aggregation and inhibited adsorption through blocking available adsorption sites. The findings further demonstrate the complex mechanisms controlling interactions between nC60 and organic contaminants, and may have significant implications for the life-cycle analysis and risk assessment of C60.

  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. 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.

  12. High-field ESR in TDAE-C60

    NASA Astrophysics Data System (ADS)

    Blinc, R.; Cevc, P.; Arčon, D.; Omerzu, A.; Mehring, M.; Knorr, S.; Grupp, A.; Barra, A.-L.; Chouteau, G.

    1998-12-01

    The ESR spectra of TDAE-C60 single crystals have been measured between 30 MHz and 245 GHz both above and below Tc=16 K. No separate TDAE+ ESR signal has been seen even at high fields suggesting that the TDAE+ and C-60 spins are either strongly exchange coupled or that spin cancellation and charge separation of the TDAE ions take place. The nonlinear variation of the resonance frequency versus resonance field relation characteristic of ferromagnetic resonance has been observed only in the radio frequency but not in the microwave region. No second ``hard'' mode characteristic for a spin-canted ``weak'' ferromagnet could be observed between 0 and 100 kG. The additional fine structure seen in the high-field ESR spectra below Tc is due to standing spin-wave resonance. It allows for the determination of the exchange coupling constant J=60 K. The exchange field HE=448 kG is thus much larger than the anisotropy field HK=29 G determined from the ferromagnetic resonance data. The temperature dependence of the magnetization determined from the spin-wave resonance data can be indeed described by the Bloch T3/2 law as expected for an isotropic or nearly isotropic Heisenberg ferromagnet.

  13. Thermodynamics of hydration of fullerols [C60(OH)n] and hydrogen bond dynamics in their hydration shells

    NASA Astrophysics Data System (ADS)

    Keshri, Sonanki; Tembe, B. L.

    2017-02-01

    Molecular dynamics simulations of fullerene and fullerols [C60(OH)n, where n = 2-30] in aqueous solutions have been performed for the purpose of obtaining a detailed understanding of the structural and dynamic properties of these nanoparticles in water. The structures, dynamics and hydration free energies of the solute molecules in water have been analysed. Radial distribution functions, spatial density distribution functions and hydrogen bond analyses are employed to characterize the solvation shells of water around the central solute molecules. We have found that water molecules form two solvation shells around the central solute molecule. Hydrogen bonding in the bulk solvent is unaffected by increasing n. The large decrease in solvation enthalpies of these solute molecules for n > 14 enhances solubilisation. The diffusion constants of solute molecules decrease with increasing n. The solvation free energy of C60 in water is positive (52.8 kJ/mol), whereas its value for C60(OH)30 is highly negative (-427.1 kJ/mol). The effects of surface hydroxylation become more dominant once the fullerols become soluble.

  14. Self-stability of C60 nanocapsules with radio-iodide content and its interaction with calcium atoms.

    PubMed

    Valderrama, Alejandro; Reynoso, Radamés; Gómez, Raúl W; Marquina, Vivianne

    2016-01-01

    This paper inquires the C60 capabilities to contain radio-iodide ((131)I2) molecules. The encapsulation conditions are investigated applying first principles method to simulate with geometric optimizations and molecular dynamics at 310 K and atmospheric pressure. We find that the n(131)I2@C60 system, where n = 1, 2, 3…, is stable if the content does not exceed three molecules of radio-iodide. The application of density functional theory allows us to determine that, the nanocapsules content limit is related with the amount of charge that is transferred from the iodine (131)I2 molecules to the carbon atoms in the fullerene surface. The Mulliken population analysis reveals that the excess of charge increases the repulsive forces between atoms and the bond length average in the C60 structure. The weakened bonds easily break and will critically damage the encapsulation properties. Additionally, we test the interaction nanocapsules with different amounts of radioactive iodine diatomic molecules content with calcium atoms, and find that only the fullerene containing one radioactive iodine diatomic molecule was able to interact with up to nine atoms of calcium without disrupting or cracking. Other fullerenes with two and three radio iodine diatomic molecules cannot resist the interaction with a single calcium atom without cracking or being broken.

  15. Tuning the depth of bowl-shaped phosphine hosts: capsule and pseudo-cage architectures in host-guest complexes with C60 fullerene.

    PubMed

    Yamamura, Masaki; Sukegawa, Kimiya; Nabeshima, Tatsuya

    2015-08-04

    Bowl-shaped phosphine molecules, whose bowl geometry can be controlled by a variation of the axial substituent, were synthesized, and used as host molecules to encapsulate C60. Host molecules with relatively shallow bowls formed a chiral capsule, while hosts with deeper bowls formed an achiral pseudo-cage.

  16. 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.

  17. Expansion Hamiltonian model for a diatomic molecule adsorbed on a surface: Vibrational states of the CO/Cu(100) system including surface vibrations

    NASA Astrophysics Data System (ADS)

    Meng, Qingyong; Meyer, Hans-Dieter

    2015-10-01

    Molecular-surface studies are often done by assuming a corrugated, static (i.e., rigid) surface. To be able to investigate the effects that vibrations of surface atoms may have on spectra and cross sections, an expansion Hamiltonian model is proposed on the basis of the recently reported [R. Marquardt et al., J. Chem. Phys. 132, 074108 (2010)] SAP potential energy surface (PES), which was built for the CO/Cu(100) system with a rigid surface. In contrast to other molecule-surface coupling models, such as the modified surface oscillator model, the coupling between the adsorbed molecule and the surface atoms is already included in the present expansion SAP-PES model, in which a Taylor expansion around the equilibrium positions of the surface atoms is performed. To test the quality of the Taylor expansion, a direct model, that is avoiding the expansion, is also studied. The latter, however, requests that there is only one movable surface atom included. On the basis of the present expansion and direct models, the effects of a moving top copper atom (the one to which CO is bound) on the energy levels of a bound CO/Cu(100) system are studied. For this purpose, the multiconfiguration time-dependent Hartree calculations are carried out to obtain the vibrational fundamentals and overtones of the CO/Cu(100) system including a movable top copper atom. In order to interpret the results, a simple model consisting of two coupled harmonic oscillators is introduced. From these calculations, the vibrational levels of the CO/Cu(100) system as function of the frequency of the top copper atom are discussed.

  18. Expansion Hamiltonian model for a diatomic molecule adsorbed on a surface: Vibrational states of the CO/Cu(100) system including surface vibrations

    SciTech Connect

    Meng, Qingyong; Meyer, Hans-Dieter

    2015-10-28

    Molecular-surface studies are often done by assuming a corrugated, static (i.e., rigid) surface. To be able to investigate the effects that vibrations of surface atoms may have on spectra and cross sections, an expansion Hamiltonian model is proposed on the basis of the recently reported [R. Marquardt et al., J. Chem. Phys. 132, 074108 (2010)] SAP potential energy surface (PES), which was built for the CO/Cu(100) system with a rigid surface. In contrast to other molecule-surface coupling models, such as the modified surface oscillator model, the coupling between the adsorbed molecule and the surface atoms is already included in the present expansion SAP-PES model, in which a Taylor expansion around the equilibrium positions of the surface atoms is performed. To test the quality of the Taylor expansion, a direct model, that is avoiding the expansion, is also studied. The latter, however, requests that there is only one movable surface atom included. On the basis of the present expansion and direct models, the effects of a moving top copper atom (the one to which CO is bound) on the energy levels of a bound CO/Cu(100) system are studied. For this purpose, the multiconfiguration time-dependent Hartree calculations are carried out to obtain the vibrational fundamentals and overtones of the CO/Cu(100) system including a movable top copper atom. In order to interpret the results, a simple model consisting of two coupled harmonic oscillators is introduced. From these calculations, the vibrational levels of the CO/Cu(100) system as function of the frequency of the top copper atom are discussed.

  19. Reactions of Fe+ coordinated to the [pi]-donating ligands C2H4, c-C5H5, C6H6 and C60 with N2O and CO: probing the bonding in (C60)Fe+

    NASA Astrophysics Data System (ADS)

    Baranov, Vladimir; Bohme, Diethard K.

    1995-11-01

    Experimental results are reported for gas-phase reactions of Fe+ coordinated to the [pi]-donating ligands C2H4, c-C5H5, C6H6 and C60 with N2O and CO. Reaction rate coefficients and product distributions were measured with the selected-ion flow tube (SIFT) technique operating at 294 ± 3 K and a helium buffer gas pressure of 0.35 ± 0.01 Torr. The measurements provide intrinsic efficiencies for the primary and higher-order ligation of these XFe+ cations with CO and N2O and their corresponding coordination numbers. The coordination numbers are consistent with known ground state electronic structures. Many of the ligated ions were synthesized by ion/molecule ligation reactions in the gas phase for the first time, including XFe(CO)n+ and XFe(N2O)+ with X = C2H4, c-C5H5 and C6H6, (C60)Fe(N2O)+, (C60)FeO+ and (C60)FeO(N2O)+. Also, the measurements provided an experimental assessment of the mode of bonding in (C60)Fe+.

  20. High-Pressure Synthesis of Superhard Material from C60

    NASA Astrophysics Data System (ADS)

    Horikawa, Takashi; Suito, Kaichi; Kobayashi, Michihiro; Oshima, Ryuichiro

    2005-05-01

    Fullerene, C60, has been investigated at a high pressure of 15 GPa and at a high temperature of 800°C using an octahedral anvil press. Samples retrieved after being heated to temperatures between 165 and 700°C under pressures from 10 to 15 GPa were found to be very hard, exhibiting micro-Vickers hardness ranging from 40 to 100 GPa. The hardness was governed by the pressure and temperature conditions studied as well as the duration of the high-temperature treatment. X-ray diffraction analysis and Raman scattering studies revealed that the hard products contained amorphous carbon consisting of sp2-bonded clusters with a small persistence of unknown phase.

  1. Measurement of laser activated electron tunneling from semiconductor zinc oxide to adsorbed organic molecules by a matrix assisted laser desorption ionization mass spectrometer.

    PubMed

    Zhong, Hongying; Fu, Jieying; Wang, Xiaoli; Zheng, Shi

    2012-06-04

    Measurement of light induced heterogeneous electron transfer is important for understanding of fundamental processes involved in chemistry, physics and biology, which is still challenging by current techniques. Laser activated electron tunneling (LAET) from semiconductor metal oxides was observed and characterized by a MALDI (matrix assisted laser desorption ionization) mass spectrometer in this work. Nanoparticles of ZnO were placed on a MALDI sample plate. Free fatty acids and derivatives were used as models of organic compounds and directly deposited on the surface of ZnO nanoparticles. Irradiation of UV laser (λ=355 nm) with energy more than the band gap of ZnO produces ions that can be detected in negative mode. When TiO(2) nanoparticles with similar band gap but much lower electron mobility were used, these ions were not observed unless the voltage on the sample plate was increased. The experimental results indicate that laser induced electron tunneling is dependent on the electron mobility and the strength of the electric field. Capture of low energy electrons by charge-deficient atoms of adsorbed organic molecules causes unpaired electron-directed cleavages of chemical bonds in a nonergodic pathway. In positive detection mode, electron tunneling cannot be observed due to the reverse moving direction of electrons. It should be able to expect that laser desorption ionization mass spectrometry is a new technique capable of probing the dynamics of electron tunneling. LAET offers advantages as a new ionization dissociation method for mass spectrometry.

  2. 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.

  3. Perspective: C60+ and laboratory spectroscopy related to diffuse interstellar bands

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

    In the last 30 years, our research has focused on laboratory measurements of the electronic spectra of organic radicals and ions. Many of the species investigated were selected based on their potential astrophysical relevance, particularly in connection with the identification of appealing candidate molecules for the diffuse interstellar absorptions. Notably, carbon chains and derivatives containing hydrogen and nitrogen atoms in their neutral and ionic forms were studied. These data could be obtained after developing appropriate techniques to record spectra at low temperatures relevant to the interstellar medium. The measurement of gas phase laboratory spectra has enabled direct comparisons with astronomical data to be made and though many species were found to have electronic transitions in the visible where the majority of diffuse bands are observed, none of the absorptions matched the prominent interstellar features. In 2015, however, the first carrier molecule was identified: C60 + . This was achieved after the measurement of the electronic spectrum of C60 + -He at 6K in a radiofrequency ion trap.

  4. First-principles investigation on the geometry and electronic structure of the three-dimensional cuboidal C(60) polymer.

    PubMed

    Yang, Jianjun; Tse, John S; Iitaka, Toshiaki

    2007-10-07

    The structural stability and electronic properties of the recently characterized three-dimensional (3D) cuboid-shaped C(60) polymer are studied using periodic ab initio density functional methods. It is shown that the experimentally observed structure is metastable and not fully relaxed from the high pressure state. A second polymorph, which is more stable than the experimental structure, is identified from the calculations. This new structure differs from the observed structure in the number of fourfold-coordinated atoms per C(60) molecule. Both structures are found to be metallic with bulk moduli only about one-third that of diamond. The cuboidal C(60) is not the long sought after superhard 3D carbon polymer; however, the two polymorphs studied here reveal unusual electronic band structures that might suggest interesting electronic properties.

  5. First-principles investigation on the geometry and electronic structure of the three-dimensional cuboidal C60 polymer

    NASA Astrophysics Data System (ADS)

    Yang, Jianjun; Tse, John S.; Iitaka, Toshiaki

    2007-10-01

    The structural stability and electronic properties of the recently characterized three-dimensional (3D) cuboid-shaped C60 polymer are studied using periodic ab initio density functional methods. It is shown that the experimentally observed structure is metastable and not fully relaxed from the high pressure state. A second polymorph, which is more stable than the experimental structure, is identified from the calculations. This new structure differs from the observed structure in the number of fourfold-coordinated atoms per C60 molecule. Both structures are found to be metallic with bulk moduli only about one-third that of diamond. The cuboidal C60 is not the long sought after superhard 3D carbon polymer; however, the two polymorphs studied here reveal unusual electronic band structures that might suggest interesting electronic properties.

  6. Dual electron transfer pathways from the excited C60 radical anion: enhanced reactivities due to the photoexcitation of reaction intermediates.

    PubMed

    Fujitsuka, Mamoru; Ohsaka, Tatsuya; Majima, Tetsuro

    2015-12-14

    In the present study, electron transfer (ET) processes from excited radical anions have been investigated using dyad molecules including C60. The deactivation process of excited C60˙(-), including the internal conversion from the D1 to the D0 state and the cooling process of the vibrationally hot ground state (D), was observed spectroscopically for the first time. These processes could be unambiguously distinguished by the observation of the stimulated emission from the D1 state. The intramolecular ET processes from the excited C60˙(-) were confirmed by the transient absorption spectra. Clearly, both D1 and D states acted as precursors for the ET, i.e., dual ET pathways were confirmed. The driving force dependence of the ET rates was well characterized by the Marcus theory, which revealed that the forward ET processes are located at the top region of the Marcus parabola. In addition, the ET from the excited imide radical anion to C60 and that from the ground state C60˙(-) to imide were examined. The ET rate from the excited imide radical anion and that from ground state C60˙(-) did not follow the Marcus parabola estimated for the ET from the excited C60˙(-). The observed difference can be attributed to the difference in the energy required to form the reduced spacer (Δ) in the superexchange mechanism. Because the Δ value tends to become smaller for ET processes from excited radical ions, fast and efficient ET processes are expected from these states as demonstrated in the present study.

  7. The effect of solvent ratio and water on the growth of C 60 nanowhiskers

    NASA Astrophysics Data System (ADS)

    Miyazawa, Kun'ichi; Hotta, Kayoko

    2010-09-01

    The growth of C 60 nanowhiskers (C 60NWs) prepared by a modified liquid-liquid interfacial precipitation method is investigated, focusing on the effect of solvent ratio and water content in the C 60-toluene-isopropyl alcohol (IPA) solution system. The precipitation of C 60NWs was markedly influenced by the solvent ratio of toluene to IPA, and the C 60NWs were found to grow longer above a critical diameter ( Dc), which depends on the solvent ratio. The addition of a small amount of H 2O to the C 60-toluene-IPA solution promoted the growth of C 60NWs. This catalytic effect of water on the growth of C 60NWs was confirmed also by the experiment using heavy water (D 2O) and by the decrease of growth activation energy of C 60NWs with increase of H 2O content in the C 60-toluene-IPA solution.

  8. 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

  9. Graphene oxide-fullerene C60 (GO-C60) hybrid for photodynamic and photothermal therapy triggered by near-infrared light.

    PubMed

    Li, Qian; Hong, Liang; Li, Hongguang; Liu, Chenguang

    2017-03-15

    Photodynamic therapy (PDT) and photothermal therapy (PTT) are two promising methodologies for cancer therapy. Although a variety of materials which can be used in PDT and PTT have been developed in the past decades, those showing the combined effect of PDT and PTT under NIR irradiation are rare. Graphene oxide (GO) and fullerene C60 (denoted as C60 hereafter) with unique physical and chemical properties are promising candidates for PTT and PDT, respectively. Here, by using a stepwise conjugation method, a new GO-C60 hybrid which contains hydrophilic methoxypolyethylene glycol (mPEG) and mono-substituted C60 was constructed for combined PDT and PTT. The hybrid shows good solubility in different environments including physiological solutions. The introduction of C60 to GO did not decrease the photothermal properties of GO, while the conjugation of GO to C60 activated the ability of C60 to generate singlet oxygen ((1)O2) in near infrared (NIR) region in aqueous solution. The GO-C60 hybrid also shows good ability to induce the generation of reactive oxygen species (ROS) in Hela cells. Due to the synergistic effect between GO and C60, GO-C60 hybrid exhibits superior performance in the inhibition of cancer cells compared to both individuals, indicating its high potential in practical applications.

  10. Adsorption and trace detection of pharmacologically significant 5-methylthio-1, 3, 4-thiadiazole-2-thiol molecule adsorbed on silver nanocolloids and understanding the role of Albrecht's “A” and Herzberg-Teller contributions in the SERS spectra

    NASA Astrophysics Data System (ADS)

    Chowdhury, Joydeep; Chandra, Subhendu; Ghosh, Manash

    2015-01-01

    The surface enhanced Raman scattering (SERS) spectra of biologically and industrially significant 5-methylthio-1, 3, 4-thiadiazole 2-thiol molecule have been investigated. The SERS spectra at various concentrations of the adsorbate are compared with the Fourier transform Infrared (FTIR) and normal Raman spectra (NRS) of the probe molecule recorded in different environmental conditions. The optimized molecular structures of the most probable thione and the thiol forms of the molecule have been estimated from the density functional theory (DFT) calculations. The vibrational signatures of the molecule have been assigned from the potential energy distributions (PEDs). The detail vibrational analyses reveal that ∼54% of the thione form of the molecule is prevalent in the solid state and its population increases to ∼65% in ACN solvent medium. Concentration dependent SERS, together with the 2-dimensional correlation spectra (2D-COS), corroborate the presence of both the thione and the thiol forms of the molecule even in the surface adsorbed state. The orientations of the thione and the thiol forms of the molecule on the nanocolloidal silver surface have been predicted from the surface selection rule. The selective enhancement of Raman bands in the SERS spectra have been explored from the view of the Albrecht's "A" and Herzberg-Teller (HT) charge transfer (CT) contribution.

  11. Understanding the electronic structure of CdSe quantum dot-fullerene (C60) hybrid nanostructure for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Sarkar, Sunandan; Rajbanshi, Biplab; Sarkar, Pranab

    2014-09-01

    By using the density-functional tight binding method, we studied the electronic structure of CdSe quantum dot(QD)-buckminsterfullerene (C60) hybrid systems as a function of both the size of the QD and concentration of the fullerene molecule. Our calculation reveals that the lowest unoccupied molecular orbital energy level of the hybrid CdSeQD-C60 systems lies on the fullerene moiety, whereas the highest occupied molecular orbital (HOMO) energy level lies either on the QD or the fullerene depending on size of the CdSe QD. We explored the possibility of engineering the energy level alignment by varying the size of the CdSe QD. With increase in size of the QD, the HOMO level is shifted upward and crosses the HOMO level of the C60-thiol molecule resulting transition from the type-I to type-II band energy alignment. The density of states and charge density plot support these types of band gap engineering of the CdSe-C60 hybrid systems. This type II band alignment indicates the possibility of application of this nanohybrid for photovoltaic purpose.

  12. 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

  13. C60 superstructure and carbide formation on the Al-terminated Al9Co2(001 ) surface

    NASA Astrophysics Data System (ADS)

    Ledieu, J.; Gaudry, É.; de Weerd, M.-C.; Gille, P.; Diehl, R. D.; Fournée, V.

    2015-04-01

    We report the formation of an ordered C60 monolayer on the Al9Co2 (001) surface using scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), x-ray and ultraviolet photoelectron spectroscopy (XPS/UPS), and ab initio calculations. Dosing fullerenes at 300 K results in a disordered overlayer. However, the adsorption of C60 with the sample held between 573-673 K leads to a [4, -2 ∣1 ,3 ] phase. The growth of C60 proceeds with the formation of two domains which are mirror symmetric with respect to the [100] direction. Within each domain, the superstructure unit cell contains six molecules and this implies an area per fullerene equal to 91 Å2. The molecules exhibit two types of contrast (bright and dim) which are bias dependent. The adsorption energies and preferred molecular configuration at several possible adsorption sites have been determined theoretically. These calculations lead to a possible scheme describing the configuration of each C60 in the observed superstructure. Several defects (vacancies, protrusions,…) and domain boundaries observed in the film are also discussed. If the sample temperature is higher than 693 K when dosing, impinging C60 molecules dissociate at the surface, hence leading to the formation of a carbide film as observed by STM and LEED measurements. The formation of Al4C3 domains and the molecular dissociation are confirmed by XPS/UPS measurements acquired at different stages of the experiment. The cluster substructure present at the Al9Co2 (001) surface dictates the carbide domain orientations.

  14. 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.

  15. Influence of endohedral confinement of atoms on structural and dynamical properties of the C60 fullerene

    NASA Astrophysics Data System (ADS)

    Etindele, A. J.; Maezono, R.; Melingui Melono, R. L.; Motapon, O.

    2017-10-01

    The influence of encapsulated atoms in the structural and dynamical properties of C60 in A@C60 complexes is studied in the framework of the Density Functional Theory using Density of states and the theoretical Electron Energy Loss Spectroscopy. It is shown that C60 preserves its spherical geometry no matter the equilibrium position of the encapsulated atom. The Infrared and Raman spectra of the H@C60, He@C60 and Ne@C60 complexes are found not to differ significantly from that of C60 whereas those for Li@C60 and Na@C60 exhibit more peaks. The analysis shows that the changes on the cage properties come from inside it.

  16. 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.

  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. Effect of incarcerated HF on the exohedral chemical reactivity of HF@C60.

    PubMed

    Vidal, Sara; Izquierdo, Marta; Alom, Shamim; Garcia-Borràs, Marc; Filippone, Salvatore; Osuna, Sílvia; Solà, Miquel; Whitby, Richard J; Martín, Nazario

    2017-10-05

    The first chemical modification on the brand new endohedral HF@C60 is reported. In particular, the isomerization from optically pure (2S,5S)-cis-pyrrolidino[3,4:1,2][60]fullerene 2b to (2S,5R)-trans-pyrrolidino[3,4:1,2][60]fullerene 2b has been studied and compared with empty C60 (2a) and endohedral H2O@C60 (3). The comparative study shows a kinetic order for the isomerization process of H2O@C60 > HF@C60 > C60, thus confirming the effect of the incarcerated species on the zwitterionic intermediate stability.

  19. Superconductivity of Fullerides with Composition AGaxC_{60} and AGaxMyC_{60} (A = K, Rb; M = In, Sn, Bi)

    NASA Astrophysics Data System (ADS)

    Kulbachinskii, V. A.; Lunin, R. A.; Velikodny, Yu. A.; Bulychev, B. M.

    2016-12-01

    The new heterofullerides with the composition AGaxC_{60} and AGaxMyC_{60} (A = K, Rb; M = In, Sn, Bi; x,y<1) have been synthesized by a new method using liquid alloys of alkali metal with gallium or gallams. The temperature dependence of the magnetic susceptibility was measured in the temperature range from 4.2 to 100 K, and transitions to a superconducting state were observed at temperatures Tc ranging from 7 to 17.5 K. The superconductivity was found for fullerides RbGaxC_{60} and RbGaxInyC_{60} with orthorhombic lattice.

  20. C+60 Ions in Collisions with Crystalline Surfaces:. Kinematics and Dynamics

    NASA Astrophysics Data System (ADS)

    Lill, Th.; Busmann, H.-G.; Lacher, F.; Hertel, I. V.

    Collisions of C+60 ions with surfaces of highly oriented pyrolytic graphite (HOPG), diamond (111) and heteroepitaxial fullerite films on mica in the impact energy range between 100 and 1500 eV are studied by mass, energy, and angle resolved time-of-flight mass spectrometry. For the graphite and diamond surfaces, highly inelastic scattering has been observed. The analysis of the velocity dependence of the scattered ions reveals that the normal and tangential component of the ion velocity have different significance for the collision dynamics. The normal component of the velocity appears to determine the amount of energy transferred into vibrational and deformational energy of the projectile and target. The final kinetic energy is independent of the impact energy for impact angles of ≈20° and impact energies between 140 and 450 eV. This observation can be explained by the existence of an upper bound of the final kinetic energy that is defined by the amount of energy stored in the deformed molecule without being deposited or destroyed. The tangential component is partially transformed into rotational energy of the C+60 in the collision with the surface, as may be explained by a simple rolling ball model. In contrast, scattering from heteroepitaxial fullerite films is nearly elastic for impact energies up to 230 eV and impact angles of about 20°. Additionally, the velocity distributions reveal a low velocity component. Its relative intensity increases with increasing impact energy and remains the only feature in the velocity distribution for impact energies higher than 290 eV. This component is due to sputtering of surface molecules. The angular dependent intensities of the fast ions exhibit a rich structure. This can be attributed to rainbow scattering, as confirmed by classical trajectory and molecular dynamics calculations with different levels of sophistication. These calculations also show that linear collision sequences along the closed packed rows of the

  1. The transition from the ordered to the merohedral disordered phase in oxygenated solid C 60

    NASA Astrophysics Data System (ADS)

    Gu, Min; Wang, Yening; Tang, Tong B.; Zhang, Weiyi; Hu, Chen; Yan, Feng; Feng, Duan

    1996-02-01

    C 60 powder, pellets and single crystals were oxygenated at 0.11 kbar and then studied with MAS 13C NMR, DSC and XRD. In agreement with reports by other authors, powder samples exhibited minor NMR resonances, indicative of blocking of fullerene rotation by interstitial oxygen, the distribution of which had yet to attain the equilibrium state. Also, as reported by others, DSC showed two endothermic peaks near 260 K, and both, we found, corresponded to a discontinuous change in the lattice parameter. The peak on the low-temperature side moved up in temperature with elapsed time. Pellets, in which presumably oxygen diffused easily, displayed only one peak but shifted in the same manner. Single crystals, in contrast, had only the higher-temperature “immobile” peak. We suggest that the shifting endotherm originates from the transition of oxygen-intercalated C 60 to a merohedral disordered phase, in which the rotation of fullerene molecules is partially impeded by oxygen. A phenomenological model is proposed for this transition.

  2. Transition from SAMO to Rydberg State Ionization in C60 in Femtosecond Laser Fields

    PubMed Central

    2016-01-01

    The transition between two distinct ionization mechanisms in femtosecond laser fields at 785 nm is observed for C60 molecules. The transition occurs in the investigated intensity range from 3 to 20 TW/cm2 and is visualized in electron kinetic energy spectra below the one-photon energy (1.5 eV) obtained via velocity map imaging. Assignment of several observed broad spectral peaks to ionization from superatom molecular orbitals (SAMOs) and Rydberg states is based on time-dependent density functional theory simulations. We find that ionization from SAMOs dominates the spectra for intensities below 5 TW/cm2. As the intensity increases, Rydberg state ionization exceeds the prominence of SAMOs. Using short laser pulses (20 fs) allowed uncovering of distinct six-lobe photoelectron angular distributions with kinetic energies just above the threshold (below 0.2 eV), which we interpret as over-the-barrier ionization of shallow f-Rydberg states in C60. PMID:27934203

  3. Experimental and theoretical studies of novel hydrogen diffuson in fullerite C_60

    NASA Astrophysics Data System (ADS)

    Fitzgerald, Stephen; Hannachi, Rym; Sholl, David; Sieber, Kurt; Gerogiorgis, Dimitrios

    2004-03-01

    Given the present interest in hydrogen storage within novel forms of carbon we have investigated the behavior of molecular H2 within solid fullerite C_60. Although C_60 will never be a practical storage medium, it does offer an ideal system to study the interaction of hydrogen within a well-characterized curved graphitic matrix. Our results based on infrared spectroscopy and loading isotherms indicate that isolated interstitial H2 bind preferentially in the lattice octahedral sites and diffuse by hopping between octahedral and tetrahedral sites^1. Parallel replica dynamics and minimum energy path calculations reveal an unexpected diffusion mechanism involving H2 molecules hopping into an already occupied octahedral site^2. This creates a short-lived H2 dimer, with a lower activation barrier for hopping that greatly enhances the diffusion rates. These calculations have been confirmed by experimental isotherm measurements and simulations using a rigorously derived lattice model that show a greatly reduced outgassing life-time with increasing H2 concentrations. ^1 S. A. FitzGerald, S. Forth and M. Rinkoski, Phys. Rev. B, 65, 140302 (2002). ^2 B. P. Uberuaga, A. F. Voter, K. K. Sieber, and D. S. Sholl, Phys. Rev. Lett., 91, 105901 (2003).

  4. A biologically effective fullerene (C60) derivative with superoxide dismutase mimetic properties.

    PubMed

    Ali, Sameh S; Hardt, Joshua I; Quick, Kevin L; Kim-Han, Jeong Sook; Erlanger, Bernard F; Huang, Ting-Ting; Epstein, Charles J; Dugan, Laura L

    2004-10-15

    Superoxide, a potentially toxic by-product of cellular metabolism, may contribute to tissue injury in many types of human disease. Here we show that a tris-malonic acid derivative of the fullerene C60 molecule (C3) is capable of removing the biologically important superoxide radical with a rate constant (k(C3)) of 2 x 10(6) mol(-1) s(-1), approximately 100-fold slower than the superoxide dismutases (SOD), a family of enzymes responsible for endogenous dismutation of superoxide. This rate constant is within the range of values reported for several manganese-containing SOD mimetic compounds. The reaction between C3 and superoxide was not via stoichiometric "scavenging," as expected, but through catalytic dismutation of superoxide, indicated by lack of structural modifications to C3, regeneration of oxygen, production of hydrogen peroxide, and absence of EPR-active (paramagnetic) products, all consistent with a catalytic mechanism. A model is proposed in which electron-deficient regions on the C60 sphere work in concert with malonyl groups attached to C3 to electrostatically guide and stabilize superoxide, promoting dismutation. We also found that C3 treatment of Sod2(-/-) mice, which lack expression of mitochondrial manganese superoxide dismutase (MnSOD), increased their life span by 300%. These data, coupled with evidence that C3 localizes to mitochondria, suggest that C3 functionally replaces MnSOD, acting as a biologically effective SOD mimetic.

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

    NASA Astrophysics Data System (ADS)

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

    2003-08-01

    To study the influence of the flux ratio of C60 molecule to Ar cluster ion on 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.

  6. Effect of an electric field on a methane molecule. I. Infrared analysis of methane (CH4-CD4) adsorbed in NaA zeolite in the temperature range 150-20 K

    NASA Astrophysics Data System (ADS)

    De Lara, E. Cohen; Kahn, R.; Seloudoux, R.

    1985-09-01

    The spectra of methane adsorbed at low temperature in NaA zeolite show two strong effects of the field existing in the cavities: (i) the appearance of the ν1 forbidden band which increases when decreasing the temperature and (ii) the splitting of the ν3 degenerate band. The variation with T of its components lead to the conclusion that the molecule progressively is oriented in a C3V configuration with respect to the field.

  7. Adsorbent phosphates

    NASA Technical Reports Server (NTRS)

    Watanabe, S.

    1983-01-01

    An adsorbent which uses as its primary ingredient phosphoric acid salts of zirconium or titanium is presented. Production methods are discussed and several examples are detailed. Measurements of separating characteristics of some gases using the salts are given.

  8. Geochemistry and cosmochemistry of fullerenes 3: Reaction of C60 and C70 with ozone

    NASA Technical Reports Server (NTRS)

    Heymann, D.; Chibante, L. P. F.

    1993-01-01

    C60 and C70 dissolved in toluene were treated with O2 gas containing 2.6 volume percent ozone and with O3-free oxygen. No reaction products were detected for 0.1 mole of O2 passed through the solution, but destruction of C60 was clearly detectable for a dose of 10(exp -6) moles of O3. C70 was destroyed more slowly than C60. Among the substances remaining in solution, we identified C60O, C70O, C60O2, C60O3, and C60O4. C60 crystals exposed to O3 at room temperature became less soluble in toluene in a matter of days, but oxides were apparently not formed.

  9. Vibrational frequency shifts of diatomic molecules in interaction with a Na + cation by ab initio calculations. Comparison with experiment on H 2 and N 2 adsorbed in NaA zeolite

    NASA Astrophysics Data System (ADS)

    Koubi, Laure; Blain, Monique; de Lara, Evelyne Cohen; Leclerq, Jean-Marie

    1994-01-01

    Ab initio calculations on H 2 and N 2 and on the same molecules in the presence of a Na + cation are presented. The equilibrium configuration and the vibrational frequency shift due to the interaction are calculated. The potential energy surfaces are obtained by local osculatory interpolations and extrapolations. The vibrational frequencies are calculated by the Numerov—Cooley method. The direction of the frequency shift is found to be related to the orientation of the diatomic molecule with respect to the cation. The results are compared with experimental data on induced infrared bands of H 2 and N 2 adsorbed in NaA zeolite.

  10. 13C-substituted C60+: Predictions of the rotational spectra

    NASA Astrophysics Data System (ADS)

    Yamada, Koichi M. T.; Ross, Stephen C.; Ito, Fumiyuki

    2017-03-01

    C60+ has recently been identified as the carrier of some of the diffuse interstellar bands (Campbell et al., 2015). Unfortunately, this ion has no dipole moment and therefore no rotational spectrum. We investigate the situation where one of the carbon atoms in this ion is substituted by a 13C-atom. This shifts the center of mass away from the center of charge, resulting in a non-zero dipole moment and thus opening the possibility of rotational spectroscopy in the microwave region. That the population of the singly substituted species is comparable to that of the parent isotopologue increases the expected intensity. One complication is that the Jahn-Teller effect may distort the molecule. We use density functional theory to consider this possibility and the rotational properties of the different isomers that would result.

  11. Photoionization of atoms confined in C60 versus C240: Giant enhancement and attosecond delay

    NASA Astrophysics Data System (ADS)

    Magrakvelidze, Maia; Shi, Kele; Anstine, Dylan; Chakraborty, Himadri

    2015-05-01

    We investigate the effects of confinement and electron correlation on the photoemissions of noble gas atoms sequestered endohedrally in C60 versus C240. The time-dependent local density approximation (TDLDA) method with Leeuwen and Baerends (LB94) exchange-correlation functional is employed. We study the moduli and phases of the photoionization dipole matrix elements involving atomic-type as well as atom-fullerene hybrid-type levels of the molecules and extract associated cross sections and angle-integrated Wigner-Smith time-delays. We examine the size effects of the molecular cage on the plasmonically enhanced strength of the atomic ionization. Furthermore, the behavior of emission time delays in attoseconds, induced by this enhancement as well as by the confinement-modified atomic Cooper minima, as a function of fullerene size is scrutinized in detailed. This work was supported by the U.S. National Science Foundation.

  12. Electronic transitions and band offsets in C60:SubPc and C60:MgPc on MoO3 studied by modulated surface photovoltage spectroscopy

    NASA Astrophysics Data System (ADS)

    Fengler, S.; Dittrich, Th.; Rusu, M.

    2015-07-01

    Electronic transitions at interfaces between MoO3 layers and organic layers of C60, SubPc, MgPc, and nano-composite layers of SubPc:C60 and MgPc:C60 have been studied by modulated surface photovoltage (SPV) spectroscopy. For all systems, time dependent and modulated SPV signals pointed to dissociation of excitons at the MoO3/organic layer interfaces with a separation of holes towards MoO3. The highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps (EHL) of C60, SubPc, and MgPc and the effective EHL of SubPc:C60 and MgPc:C60 were measured. The offsets between the LUMO (ΔEL) or HOMO (ΔEH) bands were obtained with high precision and amounted to 0.33 or 0.73 eV for SubPc:C60, respectively, and to -0.33 or 0.67 eV for MgPc:C60, respectively. Exponential tails below EHL and most pronounced sub-bandgap transitions were characterized and ascribed to disorder and transitions from HOMO bands to unoccupied defect states.

  13. Selective supramolecular fullerene-porphyrin interactions and switching in surface-confined C60-Ce(TPP)2 dyads.

    PubMed

    Vijayaraghavan, Saranyan; Écija, David; Auwärter, Willi; Joshi, Sushobhan; Seufert, Knud; Seitsonen, Ari P; Tashiro, Kentaro; Barth, Johannes V

    2012-08-08

    The control of organic molecules, supramolecular complexes and donor-acceptor systems at interfaces is a key issue in the development of novel hybrid architectures for regulation of charge-carrier transport pathways in nanoelectronics or organic photovoltaics. However, at present little is known regarding the intricate features of stacked molecular nanostructures stabilized by noncovalent interactions. Here we explore at the single molecule level the geometry and electronic properties of model donor-acceptor dyads stabilized by van der Waals interactions on a single crystal Ag(111) support. Our combined scanning tunneling microscopy/spectroscopy (STM/STS) and first-principles computational modeling study reveals site-selective positioning of C(60) molecules on Ce(TPP)(2) porphyrin double-decker arrays with the fullerene centered on the π-system of the top bowl-shaped tetrapyrrole macrocycle. Three specific orientations of the C(60) cage in the van der Waals complex are identified that can be reversibly switched by STM manipulation protocols. Each configuration presents a distinct conductivity, which accounts for a tristable molecular switch and the tunability of the intradyad coupling. In addition, STS data evidence electronic decoupling of the hovering C(60) units from the metal substrate, a prerequisite for photophysical applications.

  14. Ab initio calculation of X-ray emission and IR spectra of the hydrofullerene C 60H 36

    NASA Astrophysics Data System (ADS)

    Bulusheva, L. G.; Okotrub, A. V.; Antich, A. V.; Lobach, A. S.

    2001-05-01

    Two isomers of the hydrofullerene C 60H 36 with T and D3 d symmetry were calculated using ab initio Hartree-Fock self-consistent field (HF-SCF). The T symmetry isomer in which the benzenoid rings occupy tetrahedral positions is predicted to be lower in energy than the other considered isomer. Simulated CK α spectra of the isomers were compared with the X-ray fluorescence spectrum of the hydrofullerene C 60H 36 prepared by the transfer hydrogenation method. The short-wave maximum intensity of the CK α spectrum of C 60H 36 was shown to be sensitive to the number of π electrons in the high-occupied levels of the molecule. Although the theoretical spectra are similar in appearance, the T isomer seems to be in better accordance with the experiment. Furthermore, the computed infrared frequencies and intensities for this isomer were found to correlate well with features in the measured spectrum of C 60H 36. The most intense peak in the low-frequency spectral region was shown to correspond to the skeletal vibrations of the benzenoid rings.

  15. Extending the range of low energy electron diffraction (LEED) surface structure determination: Co-adsorbed molecules, incommensurate overlayers and alloy surface order studied by new video and electron counting LEED techniques

    SciTech Connect

    Ogletree, D.F.

    1986-11-01

    LEED multiple scattering theory is briefly summarized, and aspects of electron scattering with particular significance to experimental measurements such as electron beam coherence, instrument response and phonon scattering are analyzed. Diffuse LEED experiments are discussed. New techniques that enhance the power of LEED are described, including a real-time video image digitizer applied to LEED intensity measurements, along with computer programs to generate I-V curves. The first electron counting LEED detector using a ''wedge and strip'' position sensitive anode and digital electronics is described. This instrument uses picoampere incident beam currents, and its sensitivity is limited only by statistics and counting times. Structural results on new classes of surface systems are presented. The structure of the c(4 x 2) phase of carbon monoxide adsorbed on Pt(111) has been determined, showing that carbon monoxide molecules adsorb in both top and bridge sites, 1.85 +- 0.10 A and 1.55 +- 0.10 A above the metal surface, respectively. The structure of an incommensurate graphite overlayer on Pt(111) is analyzed. The graphite layer is 3.70 +- 0.05 A above the metal surface, with intercalated carbon atoms located 1.25 +- 0.10 A above hollow sites supporting it. The (2..sqrt..3 x 4)-rectangular phase of benzene and carbon monoxide coadsorbed on Pt(111) is analyzed. Benzene molecules adsorb in bridge sites parallel to and 2.10 +- 0.10 A above the surface. The carbon ring is expanded, with an average C-C bond length of 1.72 +- 0.15 A. The carbon monoxide molecules also adsorb in bridge sites. The structure of the (..sqrt..3 x ..sqrt..3) reconstruction on the (111) face of the ..cap alpha..-CuAl alloy has been determined.

  16. One-step synthesis of fullerene hydride C(60)H2 via hydrolysis of acylated fullerenes.

    PubMed

    Tzirakis, Manolis D; Alberti, Mariza N; Nye, Leanne C; Drewello, Thomas; Orfanopoulos, Michael

    2009-08-07

    The hitherto unexplored class of acylated fullerene compounds has been shown to be excellent C(60)H2 precursors. Upon a simple treatment with basic Al2O3, they are hydrolyzed quantitatively into C(60)H2. This key feature led to the development of a new, straightforward protocol for the selective synthesis of the simplest [60]fullerene hydride, C(60)H2. This protocol may offer an advantageous alternative to previously known methods for the synthesis of C(60)H2 allowing for a rapid access to C(60)H2 in good yield and high purity without tedious separating processes.

  17. C60-Fullerenes: detection of intracellular photoluminescence and lack of cytotoxic effects

    PubMed Central

    Levi, Nicole; Hantgan, Roy R; Lively, Mark O; Carroll, David L; Prasad, Gaddamanugu L

    2006-01-01

    We have developed a new method of application of C60 to cultured cells that does not require water-solubilization techniques. Normal and malignant cells take-up C60 and the inherent photoluminescence of C60 is detected within multiple cell lines. Treatment of cells with up to 200 μg/ml (200 ppm) of C60 does not alter morphology, cytoskeletal organization, cell cycle dynamics nor does it inhibit cell proliferation. Our work shows that pristine C60 is non-toxic to the cells, and suggests that fullerene-based nanocarriers may be used for biomedical applications. PMID:17169152

  18. On the existence of HeHe bond in the endohedral fullerene Не2 @C60.

    PubMed

    Yu Nikolaienko, Tymofii; Kryachko, Eugene S; Dolgonos, Grygoriy A

    2017-09-06

    Twenty years have already been passed since the endohedral fullerene's void ceaselessly attracts attention of both, experimentalists and theoreticians, computational chemists and physicists in particular, who direct their efforts on computer simulations of encapsulating atoms and molecules into fullerene void and on unraveling the arising bonding patterns. We review recent developments on the endohedral He2 @C60 fullerene, on its experimental observation and on related computational works. The two latter are the main concerns in the present work: on the one hand, there experimentally exists the He dimer embedded into C60 void. On the other, computational side, each He atom exhibits a negligible charge transfer to C60 resulting in that altogether, the He dimer exists as a fractionally charged (He(+)(δ) )2 . Whether there exists a bond between these two helium atoms is the key question of the present work. Since a bond is a two-body creature, we assert that it suffices to define the bond on the basis of Löwdin's postulate of a molecule which we invoke to investigate such formation of the He dimer in a given C60 void in terms of the HeHe potential energy well. It is analytically demonstrated that this well enables to maintain at least one bound (ground) state, and therefore, according to Löwdin's postulate which is naturally anticipated within quantum theory, we infer that (He(+)(δ) )2 is a molecule, a diatomic, where two heliums are bonded to each other. Using these arguments, we also propose to extend the concept of stability of endohedral fullerenes. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  19. Structural and optical properties of highly hydroxylated fullerenes: stability of molecular domains on the C60 surface.

    PubMed

    Guirado-López, R A; Rincón, M E

    2006-10-21

    The excitation spectra and the structural properties of highly hydroxylated C(60)(OH)(x) fullerenes (so-called fullerenols) are analyzed by comparing optical absorption experiments on dilute fullerenol-water solutions with semiempirical and density functional theory electronic structure calculations. The optical spectrum of fullerenol molecules with 24-28 OH attached to the carbon surface is characterized by the existence of broad bands with reduced intensities near the ultraviolet region (below approximately 500 nm) together with a complete absence of optical transitions in the visible part of the spectra, contrasting with the intense absorption observed in C(60) solutions. Our theoretical calculations of the absorption spectra, performed within the framework of the semiempirical Zerner intermediate neglect of diatomic differential overlap method [Reviews in Computational Chemistry II, edited by K. B. Lipkowitz and D. B. Boyd (VCH, Weinheim, 1991), Chap. 8, pp. 313-316] for various gas-phase-like C(60)(OH)(26) isomers, reveal that the excitation spectra of fullerenol molecules strongly depend on the degree of surface functionalization, the precise distribution of the OH groups on the carbon structure, and the presence of impurities in the samples. Interestingly, we have surprisingly found that low energy atomic configurations are obtained when the OH groups segregate on the C(60) surface forming molecular domains of different sizes. This patchy behavior for the hydroxyl molecules on the carbon surface leads in general to the formation of fullerene compounds with closed electronic shells, large highest occupied molecular orbital-lowest unoccupied molecular orbital energy gaps, and existence of an excitation spectrum that accounts for the main qualitative features observed in the experimental data.

  20. Effect of K doping on CuPc: C60 heterojunctions

    NASA Astrophysics Data System (ADS)

    Cheng, Chiu-Ping; Chen, Wen-Yen; Wei, Ching-Hsuan; Pi, Tun-Wen

    2011-12-01

    Here, the electronic properties of K-doped copper phthalocyanine (CuPc): C60 heterojunctions are studied via synchrotron-radiation photoemission. The K-doped heterointerfaces were obtained by means of C60 on K1.5CuPc and CuPc on K3C60. The photoelectron spectra show that the potassium prefers to combine with C60. At the C60/K1.5CuPc interface, the K diffuses and transfers negative charge into the C60 overlayer, while no strong chemical reaction could be found at the CuPc/K3C60 interface. A significant shift of the vacuum level was observed in both cases, which was caused by the charge transfer for the C60/K1.5CuPc and by the induced density of interface states (IDIS) dipole for the CuPc/K3C60. The energy level diagrams show that using C60 adsorption on a K-doped CuPc film is good for the improvement of photovoltaic devices. However, the inverse process, that of CuPc on a K-doped C60, is unfavorable for the photovoltaic effect.

  1. Oxidative stress-mediated hemolytic activity of solvent exchange-prepared fullerene (C60) nanoparticles

    NASA Astrophysics Data System (ADS)

    Trpkovic, Andreja; Todorovic-Markovic, Biljana; Kleut, Duska; Misirkic, Maja; Janjetovic, Kristina; Vucicevic, Ljubica; Pantovic, Aleksandar; Jovanovic, Svetlana; Dramicanin, Miroslav; Markovic, Zoran; Trajkovic, Vladimir

    2010-09-01

    The present study investigated the hemolytic properties of fullerene (C60) nanoparticles prepared by solvent exchange using tetrahydrofuran (nC60THF), or by mechanochemically assisted complexation with macrocyclic oligosaccharide gamma-cyclodextrin (nC60CDX) or the copolymer ethylene vinyl acetate-ethylene vinyl versatate (nC60EVA-EVV). The spectrophotometrical analysis of hemoglobin release revealed that only nC60THF, but not nC60CDX or nC60EVA-EVV, was able to cause lysis of human erythrocytes in a dose- and time-dependent manner. Atomic force microscopy revealed that nC60THF-mediated hemolysis was preceded by erythrocyte shrinkage and increase in cell surface roughness. A flow cytometric analysis confirmed a decrease in erythrocyte size and demonstrated a significant increase in reactive oxygen species production in red blood cells exposed to nC60THF. The nC60THF-triggered hemolytic activity was efficiently reduced by the antioxidants N-acetylcysteine and butylated hydroxyanisole, as well as by serum albumin, the most abundant protein in human blood plasma. These data indicate that nC60THF can cause serum albumin-preventable hemolysis through oxidative stress-mediated damage of the erythrocyte membrane.

  2. Synthesis and structural analysis of C60-C70 two-component fullerene nanowhiskers

    NASA Astrophysics Data System (ADS)

    Konno, Toshio; Wakahara, Takatsugu; Miyazawa, Kun'ichi

    2015-04-01

    C60-C70 two-component fullerene nanowhiskers (C60-C70NWs) were synthesized by liquid-liquid interfacial precipitation (LLIP) using various ratios of C70 to C60 and then analyzed using a focused ion beam processing apparatus (FIB-SEM), scanning electron microscopy (SEM), Raman spectroscopy, ultraviolet-visible (UV-vis) spectroscopy, X-ray diffraction (XRD) and high-performance liquid chromatography (HPLC). Both C60 and C70 were saturated in the supernatant solutions with fullerene compositions in the mother solutions ranging from 12.4 mass% C70 to 73.4 mass% C70. C60-C70NWs contained a small amount of rhombohedral phase, indicating polymerization of C60. The solid solubility limit of C70 in the C60 matrix was found to be 13.7 mass%. In addition to fine C60-C70NWs, thick C60-C70 needle-like crystals were formed. The thick C60-C70 needle-like crystals were fractured using a molybdenum probe in the FIB. The fractured surfaces of the C60-C70 needle-like crystals showed modulated structures with chemical compositions characteristic of spinodal decomposition. The activation energy of diffusion was determined to be 37.1 kJ/mol.

  3. Synthesis of C60-decorated SWCNTs (C60-d-CNTs) and its TiO2-based nanocomposite with enhanced photocatalytic activity for hydrogen production.

    PubMed

    Chai, Bo; Peng, Tianyou; Zhang, Xiaohu; Mao, Jing; Li, Kan; Zhang, Xungao

    2013-03-14

    A novel nanostructured carbon/TiO(2) nanocomposite photocatalyst is firstly fabricated via a facile hydrothermal process by using fullerene (C(60)) decorated single-walled carbon nanotubes (SWCNTs) as carbon source, which is denoted as C(60)-d-CNTs. The obtained nanostructured carbon/TiO(2) nanocomposites are characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), UV-vis diffuse reflectance spectra (DRS), Raman spectra, X-ray photoelectron spectroscopy (XPS) and photoluminescence spectra (PL), and then are used as catalysts for photocatalytic hydrogen production. It is found that the kinds and contents of various carbon nanostructured materials (such as SWCNTs, C(60) and C(60)-d-CNTs) coupled with TiO(2) can significantly enhance the photoactivity for hydrogen production, and the 5 wt% C(60)-d-CNTs/TiO(2) nanocomposite exhibits the best performance. Experimental results suggest that the C(60)-d-CNTs as a novel carbon nanostructured material could be more beneficial for the photogenerated carrier separation than SWCNTs and C(60) when these carbon nanostructured materials are coupled with TiO(2).

  4. On observing C60+ and C602+ in laboratory and space

    NASA Astrophysics Data System (ADS)

    Strelnikov, D.; Kern, B.; Kappes, M. M.

    2015-12-01

    Recently, we have measured the IR absorptions of C60+, C60-, and C602+ in neon matrixes. Many previously unknown absorptions were established. Here we compare our laboratory IR absorption spectra for C60+ and C602+ to the IR emission spectra of several astronomical objects that show C60 emission. We find that IR bands of C60+ are possibly present in the objects Tc1, SMP SMC 16, NGC 7023, NGC 2244, and SMP LMC 02. Infrared emission features possibly due to C602+ were identified in NGC 7023. To help with future observations of fullerene-related DIBs, we also revisited the oscillator strengths of the NIR absorptions of C60+, and report significantly revised values. Additionally, we report the UV oscillator strengths of C60+.

  5. Energy level alignment between C 60 and Al using ultraviolet photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Seo, J. H.; Kang, S. J.; Kim, C. Y.; Cho, S. W.; Yoo, K.-H.; Whang, C. N.

    2006-09-01

    The energy level alignment between C 60 and Al has been investigated by using ultraviolet photoelectron spectroscopy. To obtain the interfacial electronic structure between C 60 and Al, C 60 was deposited on a clean Al substrate in a stepwise manner. The valence-band spectra were measured immediately after each step of C 60 deposition without breaking the vacuum. The measured onset of the highest occupied molecular orbital energy level was located at 1.59 eV from the Fermi level of Al. The vacuum level was shifted 0.68 eV toward lower binding energy with additional C 60 layers. The observed vacuum level shift means that the interface dipole exists at the interface between C 60 and Al. The barrier height of electron injection from Al to C 60 is 0.11 eV, which is smaller value than that of hole injection.

  6. Photochemical properties of C 60. Triplet-excited C 60 quenching by electron acceptors TCNQ and TCNE in solution. Laser photolysis study

    NASA Astrophysics Data System (ADS)

    Nadtochenko, Victor A.; Denisov, Nikolai N.; Rubtsov, Igor V.; Lobach, Anatolii S.; Moravskii, Alexander P.

    1993-06-01

    The quenching of triplet-excited 3C 60 by electron acceptors TCNQ and TCNE has been established in nonpolar toluene and moderately polar benzonitrile solutions. The quenching constants kq are 5.5 × 10 9 in toluene, 2.2 × 10 9 in benzonitrile for TCNQ and 7.9 × 10 5 in toluene, 4.2 × 10 8 (M s) -1 in benzonitrile for TCNE. The 3C 60 quenching can be explained by triplet exciplex formation. The time-resolved spectra of the C 60/TCNE system exhibit a well pronounced charge-transfer excited state [C δ60 … TCNE δ-] in benzonitrile.

  7. On structural features of fullerene C60 dissolved in carbon disulfide: Complementary study by small-angle neutron scattering and molecular dynamic simulations

    NASA Astrophysics Data System (ADS)

    Avdeev, M. V.; Tropin, T. V.; Bodnarchuk, I. A.; Yaradaikin, S. P.; Rosta, L.; Aksenov, V. L.; Bulavin, L. A.

    2010-04-01

    The parameters of fullerene C60 dissolved in carbon disulfide CS2 are analyzed by small-angle neutron scattering (SANS) in a wide interval of momentum transfer. To exclude the influence of nonequilibrium conditions, the solutions are prepared without applying shaking, stirring or ultrasound. No indication of the equilibrium cluster state of C60 (with the cluster size below 60 nm) in the final solutions is revealed. Molecular dynamic simulations are complementary used to find out the partial volume of C60 in CS2 and the scattering contribution of the solvent organization at the interface with the fullerene molecule, which is shown to be small. Among several approaches for describing SANS data the preference is given to the model, which takes into account the presence of stable C60 dimers (comprising 10% of the total particle number density) in the solution.

  8. Raman study of the photopolymer formation in the {Pt(dbdtc)2}·C60 fullerene complex and the decomposition kinetics of the photo-oligomers

    NASA Astrophysics Data System (ADS)

    Meletov, K. P.; Velkos, G.; Arvanitidis, J.; Christofilos, D.; Kourouklis, G. A.

    2017-08-01

    The photopolymer formation in the fullerene layers of the C60 complex with platinum dibenzyldithiocarbamate is reported for the first time. The photo-oligomer peaks appear in the Raman spectra near the Ag(2) mode of the C60 molecule upon sample illumination with various laser wavelengths. The photo-oligomers are unstable upon heating and revert back to the C60 monomeric state. The activation energy of the thermal decomposition, obtained from the Arrhenius dependence of the decay time constant on temperature, is (1.12 ± 0.11) eV and the photo-oligomers decompose at ∼130 °C, being more fragile than the crystalline polymers of C60.

  9. Measurement of Small Molecular Dopant F4TCNQ and C60F36 Diffusion in Organic Bilayer Architectures.

    PubMed

    Li, Jun; Rochester, Chris W; Jacobs, Ian E; Friedrich, Stephan; Stroeve, Pieter; Riede, Moritz; Moulé, Adam J

    2015-12-30

    The diffusion of molecules through and between organic layers is a serious stability concern in organic electronic devices. In this work, the temperature-dependent diffusion of molecular dopants through small molecule hole transport layers is observed. Specifically we investigate bilayer stacks of small molecules used for hole transport (MeO-TPD) and p-type dopants (F4TCNQ and C60F36) used in hole injection layers for organic light emitting diodes and hole collection electrodes for organic photovoltaics. With the use of absorbance spectroscopy, photoluminescence spectroscopy, neutron reflectometry, and near-edge X-ray absorption fine structure spectroscopy, we are able to obtain a comprehensive picture of the diffusion of fluorinated small molecules through MeO-TPD layers. F4TCNQ spontaneously diffuses into the MeO-TPD material even at room temperature, while C60F36, a much bulkier molecule, is shown to have a substantially higher morphological stability. This study highlights that the differences in size/geometry and thermal properties of small molecular dopants can have a significant impact on their diffusion in organic device architectures.

  10. Effects of exchange-correlation potentials on the density-functional description of C60 versus C240 photoionization

    NASA Astrophysics Data System (ADS)

    Choi, Jinwoo; Chang, EonHo; Anstine, Dylan M.; Madjet, Mohamed El-Amine; Chakraborty, Himadri S.

    2017-02-01

    We study the photoionization properties of the C60 versus C240 molecule in a spherical jellium frame of the density-functional method. Two prototypical approximations of the exchange-correlation (xc) functional are used: (i) the Gunnarsson-Lundqvist parametrization [Gunnarsson and Lundqvist, Phys. Rev. B 13, 4274 (1976), 10.1103/PhysRevB.13.4274] with a correction for the electron self-interaction (SIC) introduced artificially from the outset and (ii) a gradient-dependent augmentation of approximation (i) using the van Leeuwen and Baerends model potential [van Leeuwen and Baerends, Phys. Rev. A 49, 2421 (1994), 10.1103/PhysRevA.49.2421], in lieu of SIC, that restores electrons' asymptotic properties intrinsically within the formalism. Ground-state results from the two schemes for both molecules show differences in the shapes of mean-field potentials and bound-level properties. The choice of an xc scheme also significantly alters the dipole single-photoionization cross sections obtained by an ab initio method that incorporates linear-response dynamical correlations. Differences in the structures and ionization responses between C60 and C240 uncover the effect of molecular size on the underlying physics. Analysis indicates that the collective plasmon resonances with the gradient-based xc option produce results noticeably closer to the experimental data available for C60.

  11. C60 fullerene localization and membrane interactions in RAW 264.7 immortalized mouse macrophages

    NASA Astrophysics Data System (ADS)

    Russ, K. A.; Elvati, P.; Parsonage, T. L.; Dews, A.; Jarvis, J. A.; Ray, M.; Schneider, B.; Smith, P. J. S.; Williamson, P. T. F.; Violi, A.; Philbert, M. A.

    2016-02-01

    There continues to be a significant increase in the number and complexity of hydrophobic nanomaterials that are engineered for a variety of commercial purposes making human exposure a significant health concern. This study uses a combination of biophysical, biochemical and computational methods to probe potential mechanisms for uptake of C60 nanoparticles into various compartments of living immune cells. Cultures of RAW 264.7 immortalized murine macrophage were used as a canonical model of immune-competent cells that are likely to provide the first line of defense following inhalation. Modes of entry studied were endocytosis/pinocytosis and passive permeation of cellular membranes. The evidence suggests marginal uptake of C60 clusters is achieved through endocytosis/pinocytosis, and that passive diffusion into membranes provides a significant source of biologically-available nanomaterial. Computational modeling of both a single molecule and a small cluster of fullerenes predicts that low concentrations of fullerenes enter the membrane individually and produce limited perturbation; however, at higher concentrations the clusters in the membrane causes deformation of the membrane. These findings are bolstered by nuclear magnetic resonance (NMR) of model membranes that reveal deformation of the cell membrane upon exposure to high concentrations of fullerenes. The atomistic and NMR models fail to explain escape of the particle out of biological membranes, but are limited to idealized systems that do not completely recapitulate the complexity of cell membranes. The surprising contribution of passive modes of cellular entry provides new avenues for toxicological research that go beyond the pharmacological inhibition of bulk transport systems such as pinocytosis.There continues to be a significant increase in the number and complexity of hydrophobic nanomaterials that are engineered for a variety of commercial purposes making human exposure a significant health concern

  12. Dynamic solvation shell and solubility of C60 in organic solvents.

    PubMed

    Wang, Chun I; Hua, Chi C; Chen, Show A

    2014-08-21

    The notion of (static) solvation shells has recently proved fruitful in revealing key molecular factors that dictate the solubility and aggregation properties of fullerene species in polar or ionic solvent media. Using molecular dynamics schemes with carefully evaluated force fields, we have scrutinized both the static and the dynamic features of the solvation shells of single C60 particle for three nonpolar organic solvents (i.e., chloroform, toluene, and chlorobenzene) and a range of system temperatures (i.e., T = 250-330 K). The central findings have been that, while the static structures of the solvation shell remain, in general, insensitive to the effects of changing solvent type or system temperature, the dynamic behavior of solvent molecules within the shell exhibits prominent dependence on both factors. Detailed analyses led us to propose the notion of dynamically stable solvation shell, effectiveness of which can be characterized by a new physical parameter defined as the ratio of two fundamental time constants representing, respectively, the solvent relaxation (or residence) time within the first solvation shell and the characteristic time required for the fullerene particle to diffuse a distance comparable to the shell thickness. We show that, for the five (two from the literature) different solvent media and the range of system temperatures examined herein, this parameter bears a value around unity and, in particular, correlates intimately with known trends of solubility for C60 solutions. We also provide evidence revealing that, in addition to fullerene-solvent interactions, solvent-solvent interactions play an important role, too, in shaping the dynamic solvation shell, as implied by recent experimental trends.

  13. C60 fullerene localization and membrane interactions in RAW 264.7 immortalized mouse macrophages.

    PubMed

    Russ, K A; Elvati, P; Parsonage, T L; Dews, A; Jarvis, J A; Ray, M; Schneider, B; Smith, P J S; Williamson, P T F; Violi, A; Philbert, M A

    2016-02-21

    There continues to be a significant increase in the number and complexity of hydrophobic nanomaterials that are engineered for a variety of commercial purposes making human exposure a significant health concern. This study uses a combination of biophysical, biochemical and computational methods to probe potential mechanisms for uptake of C60 nanoparticles into various compartments of living immune cells. Cultures of RAW 264.7 immortalized murine macrophage were used as a canonical model of immune-competent cells that are likely to provide the first line of defense following inhalation. Modes of entry studied were endocytosis/pinocytosis and passive permeation of cellular membranes. The evidence suggests marginal uptake of C60 clusters is achieved through endocytosis/pinocytosis, and that passive diffusion into membranes provides a significant source of biologically-available nanomaterial. Computational modeling of both a single molecule and a small cluster of fullerenes predicts that low concentrations of fullerenes enter the membrane individually and produce limited perturbation; however, at higher concentrations the clusters in the membrane causes deformation of the membrane. These findings are bolstered by nuclear magnetic resonance (NMR) of model membranes that reveal deformation of the cell membrane upon exposure to high concentrations of fullerenes. The atomistic and NMR models fail to explain escape of the particle out of biological membranes, but are limited to idealized systems that do not completely recapitulate the complexity of cell membranes. The surprising contribution of passive modes of cellular entry provides new avenues for toxicological research that go beyond the pharmacological inhibition of bulk transport systems such as pinocytosis.

  14. C60 Fullerene Localization and Membrane Interactions in RAW 264.7 Immortalized Mouse Macrophages

    PubMed Central

    Russ, K. A.; Elvati, P.; Parsonage, T. L.; Dews, A.; Jarvis, J. A.; Ray, M.; Schneider, B.; Smith, P. J. S.; Williamson, P. T. F.; Violi, A.; Philbert, M. A.

    2016-01-01

    There continues to be a significant increase in the number and complexity of hydrophobic nanomaterials that are engineered for a variety of commercial purposes making human exposure a significant health concern. This study uses a combination of biophysical, biochemical and computational methods to probe potential mechanisms for uptake of C60 nanoparticles into various compartments of living immune cells. Cultures of RAW 264.7 immortalized murine macrophage were used as a canonical model of immune-competent cells that are likely to provide the first line of defense following inhalation. Modes of entry studied were endocytosis/pinocytosis and passive permeation of cellular membranes. The evidence suggests marginal uptake of C60 clusters is achieved through endocytosis/pinocytosis, and that passive diffusion into membranes provides a significant source of biologically-available nanomaterial. Computational modeling of both a single molecule and a small cluster of fullerenes predicts that low concentrations of fullerenes enter the membrane individually and produce limited perturbation; however, at higher concentrations the clusters in the membrane causes deformation of the membrane. These findings are bolstered by nuclear magnetic resonance (NMR) of model membranes that reveal deformation of the cell membrane upon exposure to high concentrations of fullerenes. The atomistic and NMR models fail to explain escape of the particle out of biological membranes, but are limited to idealized systems that do not completely recapitulate the complexity of cell membranes. The surprising contribution of passive modes of cellular entry provides new avenues for toxicological research that go beyond the pharmacological inhibition of bulk transport systems such as pinocytosis. PMID:26866469

  15. Formation of a new adduct based on fullerene tris-malonate samarium salt C60-[C60(=C(COO)2)3]Sm2

    NASA Astrophysics Data System (ADS)

    Petrov, A. A.; Keskinov, V. A.; Semenov, K. N.; Charykov, N. A.; Letenko, D. G.; Nikitin, V. A.

    2017-03-01

    Gram quantities of a new adduct based on light fullerene tris-malonate samarium salt C60 [C60(=C(COO)2)3]Sm2 are obtained via the reaction of ion exchange. The obtained adduct is studied by means of electron and infrared spectroscopy, X-ray and elemental analysis, electron microscopy, and thermogravimetry. The polythermal solubility of [C60(=C(COO)2)3]Sm2 in water is determined in ampoules via saturation within 20-70°C. The composition of crystalline hydrate [C60(=C(COO)2)3]Sm2 · 36H2O, which exists in equilibrium with the saturated solution, is estimated.

  16. Electron spin density distribution in the polymer phase of CsC60: Assignment of the NMR spectrum

    NASA Astrophysics Data System (ADS)

    de Swiet, Thomas M.

    2000-11-01

    I have recently been involved in a project which used high resolution 133Cs-13C double resonance NMR data and 13C-13C NMR correlation spectra to make a partial assignment of the lines in the 13C NMR spectrum of CsC60 to the carbon positions on the C60 molecule. (T. M. de Swiet, J. L. Yarger, T. Wagberg, J. Hone, B. J. Gross, M. Tomaselli, J. J. Titman, A. Zettl and M. Mehring Phys. Rev. Lett. 84, 717 (2000)) A completion of the assignment was made on the basis of an ab initio calculation. Here I discuss this work with the emphasis on some of the previously unpublished aspects of the data analysis.

  17. Largely enhanced thermal and mechanical properties of polymer nanocomposites via incorporating C60@graphene nanocarbon hybrid

    NASA Astrophysics Data System (ADS)

    Song, Ping'an; Liu, Lina; Huang, Guobo; Yu, Youming; Guo, Qipeng

    2013-12-01

    Although considerable progress has been achieved to create advanced polymer nanocomposites using nanocarbons including fullerene (C60) and graphene, it remains a major challenge to effectively disperse them in a polymer matrix and to fully exert their extraordinary properties. Here we report a novel approach to fabricate the C60@graphene nanocarbon hybrid (C60: ˜47.9 wt%, graphene: ˜35.1%) via three-step reactions. The presence of C60 on a graphene sheet surface can effectively prevent the aggregation of the latter which in turn helps the dispersion of the former in a polymer matrix during melt-processing. C60@graphene is found to be uniformly dispersed in a polypropylene (PP) matrix. Compared with pristine C60 or graphene, C60@graphene further improves the thermal stability and mechanical properties of PP. The incorporation of 2.0 wt% C60@graphene (relative to PP) can remarkably increase the initial degradation temperature by around 59 ° C and simultaneously enhance the tensile strength and Young’s modulus by 67% and 76%, respectively, all of which are higher than those of corresponding PP/C60 (graphene) nanocomposites. These significant performance improvements are mainly due to the free-radical-trapping effect of C60, and the thermal barrier and reinforcing effects of graphene nanosheets as well as the effective stress load transfer. This work provides a new methodology to design multifunctional nanohybrids for creating advanced materials.

  18. Dispersion of C(60) in natural water and removal by conventional drinking water treatment processes.

    PubMed

    Hyung, Hoon; Kim, Jae-Hong

    2009-05-01

    The first objective of this study is to examine the fate of C(60) under two disposal scenarios through which pristine C(60) is introduced to water containing natural organic matter (NOM). A method based on liquid-liquid extraction and HPLC to quantify nC(60) in water containing NOM was also developed. When pristine C(60) was added to water either in the form of dry C(60) or in organic solvent, it formed water stable aggregates with characteristics similar to nC(60) prepared by other methods reported in the literature. The second objective of this study is to examine the fate of the nC(60) in water treatment processes, which are the first line of defense against ingestion from potable water -- a potential route for direct human consumption. Results obtained from jar tests suggested that these colloidal aggregates of C(60) were efficiently removed by a series of alum coagulation, flocculation, sedimentation and filtration processes, while the efficiency of removal dependent on various parameters such as pH, alkalinity, NOM contents and coagulant dosage. Colloidal aggregates of functionalized C(60) could be well removed by the conventional water treatment processes but with lesser efficiency compared to those made of pristine C(60).

  19. Inhalation toxicity and lung toxicokinetics of C60 fullerene nanoparticles and microparticles.

    PubMed

    Baker, Gregory L; Gupta, Amit; Clark, Mark L; Valenzuela, Blandina R; Staska, Lauren M; Harbo, Sam J; Pierce, Judy T; Dill, Jeffery A

    2008-01-01

    While several recent reports have described the toxicity of water-soluble C60 fullerene nanoparticles, none have reported the toxicity resulting from the inhalation exposures to C60 fullerene nanoparticles or microparticles. To address this knowledge gap, we exposed male rats to C60 fullerene nanoparticles (2.22 mg/m3, 55 nm diameter) and microparticles (2.35 mg/m3, 0.93 microm diameter) for 3 h a day, for 10 consecutive days using a nose-only exposure system. Nanoparticles were created utilizing an aerosol vaporization and condensation process. Nanoparticles and microparticles were subjected to high-pressure liquid chromatography (HPLC), XRD, and scanning laser Raman spectroscopy, which cumulatively indicated no chemical modification of the C60 fullerenes occurred during the aerosol generation. At necropsy, no gross or microscopic lesions were observed in either group of C60 fullerene exposures rats. Hematology and serum chemistry results found statistically significant differences, although small in magnitude, in both exposure groups. Comparisons of bronchoalveolar (BAL) lavage fluid parameters identified a significant increase in protein concentration in rats exposed to C60 fullerene nanoparticles. BAL fluid macrophages from both exposure groups contained brown pigments, consistent with C60 fullerenes. C60 lung particle burdens were greater in nanoparticle-exposed rats than in microparticle-exposed rats. The calculated lung deposition rate and deposition fraction were 41 and 50% greater, respectively, in C60 fullerene nanoparticle-exposed group than the C60 fullerene microparticle-exposed group. Lung half-lives for C60 fullerene nanoparticles and microparticles were 26 and 29 days, respectively. In summary, this first in vivo assessment of the toxicity resulting from inhalation exposures to C60 fullerene nanoparticles and microparticles found minimal changes in the toxicological endpoints examined. Additional toxicological assessments involving longer duration

  20. Distribution and biomarker of carbon-14 labeled fullerene C60 ([(14) C(U)]C60 ) in pregnant and lactating rats and their offspring after maternal intravenous exposure.

    PubMed

    Snyder, Rodney W; Fennell, Timothy R; Wingard, Christopher J; Mortensen, Ninell P; Holland, Nathan A; Shannahan, Jonathan H; Pathmasiri, Wimal; Lewin, Anita H; Sumner, Susan C J

    2015-12-01

    A comprehensive distribution study was conducted in pregnant and lactating rats exposed to a suspension of uniformly carbon-14 labeled C60 ([(14) C(U)]C60 ). Rats were administered [(14) C(U)]C60 (~0.2 mg [(14) C(U)]C60 kg(-1) body weight) or 5% polyvinylpyrrolidone (PVP)-saline vehicle via a single tail vein injection. Pregnant rats were injected on gestation day (GD) 11 (terminated with fetuses after either 24 h or 8 days), GD15 (terminated after 24 h or 4 days), or GD18 (terminated after 24 h). Lactating rats were injected on postnatal day 8 and terminated after 24 h, 3 or 11 days. The distribution of radioactivity in pregnant dams was influenced by both the state of pregnancy and time of termination after exposure. The percentage of recovered radioactivity in pregnant and lactating rats was highest in the liver and lungs. Radioactivity was quantitated in over 20 tissues. Radioactivity was found in the placenta and in fetuses of pregnant dams, and in the milk of lactating rats and in pups. Elimination of radioactivity was < 2% in urine and feces at each time point. Radioactivity remained in blood circulation up to 11 days after [(14) C(U)]C60 exposure. Biomarkers of inflammation, cardiovascular injury and oxidative stress were measured to study the biological impacts of [(14) C(U)]C60 exposure. Oxidative stress was elevated in female pups of exposed dams. Metabolomics analysis of urine showed that [(14) C(U)]C60 exposure to pregnant rats impacted the pathways of vitamin B, regulation of lipid and sugar metabolism and aminoacyl-tRNA biosynthesis. This study demonstrated that [(14) C(U)]C60 crosses the placenta at all stages of pregnancy examined, and is transferred to pups via milk.

  1. Distribution and Biomarker of Carbon-14 Labeled Fullerene C60 ([14C(U)]C60) in Pregnant and Lactating Rats and their Offspring after Maternal Intravenous Exposure

    PubMed Central

    Snyder, Rodney W.; Fennell, Timothy R.; Wingard, Christopher J.; Mortensen, Ninell P.; Holland, Nathan A.; Shannahan, Jonathan H.; Pathmasiri, Wimal; Lewin, Anita H.; Sumner, Susan C. J.

    2015-01-01

    A comprehensive distribution study was conducted in pregnant and lactating rats exposed to a suspension of uniformly carbon-14 labeled C60 ([14C(U)]C60). Rats were administered [14C(U)]C60 (~0.2 mg [14C(U)]C60/kg body weight) or 5% polyvinylpyrrolidone (PVP)-saline vehicle via a single tail vein injection. Pregnant rats were injected on gestation day (GD) 11 (terminated with fetuses after either 24h or 8d), GD15 (terminated after 24h or 4d), or GD18 (terminated after 24h). Lactating rats were injected on postnatal day 8 and terminated after 24h, 3d or 11d. The distribution of radioactivity in pregnant dams was influenced by both the state of pregnancy and time of termination after exposure. The percentage of recovered radioactivity in pregnant and lactating rats was highest in liver and lungs. Radioactivity was quantitated in over 20 tissues. Radioactivity was found in placenta and in fetuses of pregnant dams, and in the milk of lactating rats and in pups. Elimination of radioactivity was <2% in urine and feces at each time point. Radioactivity remained in blood circulation up to 11 days after [14C(U)]C60 exposure. Biomarkers of inflammation, cardiovascular injury and oxidative stress were measured to study the biological impacts of [14C(U)]C60 exposure. Oxidative stress were elevated in female pups of exposed dams. Metabolomics analysis of urine showed that [14C(U)]C60 exposure to pregnant rats impacted the pathways of vitamin B, regulation of lipid and sugar metabolism and aminoacyl-tRNA biosynthesis. This study demonstrated that [14C(U)]C60 crosses the placenta at all stages of pregnancy examined, and is transferred to pups via milk. PMID:26081520

  2. Sputtering of octatetraene by 15 keV C60 projectiles: Comparison of reactive interatomic potentials

    NASA Astrophysics Data System (ADS)

    Kanski, Michal; Maciazek, Dawid; Golunski, Mikolaj; Postawa, Zbigniew

    2017-02-01

    Molecular dynamics computer simulations have been used to probe the effect of the AIREBO, ReaxFF and COMB3 interatomic potentials on sputtering of an organic sample composed of octatetraene molecules. The system is bombarded by a 15 keV C60 projectile at normal incidence. The effect of the applied force fields on the total time of simulation, the calculated sputtering yield and the angular distribution of sputtered particles is investigated and discussed. It has been found that caution should be taken when simulating particles ejection from nonhomogeneous systems that undergo significant fragmentation described by the ReaxFF. In this case, the charge state of many particles is improper due to an inadequacy of a procedure used for calculating partial charges on atoms in molecules for conditions present during sputtering. A two-step simulation procedure is proposed to minimize the effect of this deficiency. There is also a possible problem with the COMB3 potential, at least at conditions present during cluster impact, as its results are very different from AIREBO or ReaxFF.

  3. Synthesis, crystal structure and photoconductivity of the first [60]fullerene complex with metal diethyldithiocarbamate: {CuII(dedtc)2}2.C60.

    PubMed

    Konarev, Dmitri V; Kovalevsky, Andrey Y; Lopatin, Dmitri V; Umrikhin, Alexey V; Yudanova, Evgeniya I; Coppens, Philip; Lyubovskaya, Rimma N; Saito, Gunzi

    2005-05-21

    The first molecular complex of fullerene C60 with metal dithiocarbamate, namely, {CuII(dedtc)2}2.C60(dedtc: diethyldithiocarbamate) (1) was obtained as single crystals. Butterfly-shaped CuII(dedtc)2 molecules efficiently co-crystallized with spherical fullerene molecules to form a layered structure, in which closely packed hexagonal C60 layers alternate with the layers composed of CuII(dedtc)2 dimers. The formation of the complex with C60 changes geometry and the EPR spectrum of starting CuII(dedtc)2. Magnetic susceptibility of 1 follows the Curie-Weiss law in the 300-1.9 K range with the negative Weiss constant of -2.5 K showing a weak antiferromagnetic interaction between CuII centers in the dimers. The crystals of 1 have low dark conductivity of 10(-11) S cm-1, which is consistent with a neutral ground state of the complex. Illumination of the crystals by white light increases the photocurrent by 20-50 times. The photoconductivity spectrum of 1 has a maximum at 470 nm showing that both intermolecular charge transfer between neighboring C60 molecules and photoexcitation of CuII(dedtc)2 can contribute to photogeneration of free charge carriers. The effect of a weak magnetic field with Bo<0.5 T on the photoconductivity of 1 has been found.

  4. The spin chemistry and magnetic resonance of H2@C60. From the Pauli principle to trapping a long lived nuclear excited spin state inside a buckyball.

    PubMed

    Turro, Nicholas J; Chen, Judy Y-C; Sartori, Elena; Ruzzi, Marco; Marti, Angel; Lawler, Ronald; Jockusch, Steffen; López-Gejo, Juan; Komatsu, Koichi; Murata, Yasujiro

    2010-02-16

    One of the early triumphs of quantum mechanics was Heisenberg's prediction, based on the Pauli principle and wave function symmetry arguments, that the simplest molecule, H(2), should exist as two distinct species-allotropes of elemental hydrogen. One allotrope, termed para-H(2) (pH(2)), was predicted to be a lower energy species that could be visualized as rotating like a sphere and possessing antiparallel ( upward arrow downward arrow) nuclear spins; the other allotrope, termed ortho-H(2) (oH(2)), was predicted to be a higher energy state that could be visualized as rotating like a cartwheel and possessing parallel ( upward arrow upward arrow) nuclear spins. This remarkable prediction was confirmed by the early 1930s, and pH(2) and oH(2) were not only separated and characterized but were also found to be stable almost indefinitely in the absence of paramagnetic "spin catalysts", such as molecular oxygen, or traces of paramagnetic impurities, such as metal ions. The two allotropes of elemental hydrogen, pH(2) and oH(2), may be quantitatively incarcerated in C(60) to form endofullerene guest@host complexes, symbolized as pH(2)@C(60) and oH(2)@C(60), respectively. How does the subtle difference in nuclear spin manifest itself when hydrogen allotropes are incarcerated in a buckyball? Can the incarcerated "guests" communicate with the outside world and vice versa? Can a paramagnetic spin catalyst in the outside world cause the interconversion of the allotropes and thereby effect a chemical transformation inside a buckyball? How close are the measurable properties of H(2)@C(60) to those computed for the "quantum particle in a spherical box"? Are there any potential practical applications of this fascinating marriage of the simplest molecule, H(2), with one of the most beautiful of all molecules, C(60)? How can one address such questions theoretically and experimentally? A goal of our studies is to produce an understanding of how the H(2) guest molecules incarcerated in

  5. Positively and Negatively Charged Cesium and (C60) m Cs n Cluster Ions.

    PubMed

    Renzler, Michael; Kranabetter, Lorenz; Goulart, Marcelo; Scheier, Paul; Echt, Olof

    2017-05-25

    We report on the formation and ionization of cesium and C60Cs clusters in superfluid helium nanodroplets. Size distributions of positively and negatively charged (C60) m Cs n(±) ions have been measured for m ≤ 7, n ≤ 12. Reproducible intensity anomalies are observed in high-resolution mass spectra. For both charge states, (C60) m Cs3(±) and (C60) m Cs5(±) are particularly abundant, with little dependence on the value of m. Distributions of bare cesium cluster ions also indicate enhanced stability of Cs3(±) and Cs5(±), in agreement with theoretical predictions. These findings contrast with earlier reports on highly Cs-doped cationic fullerene aggregates which showed enhanced stability of C60Cs6 building blocks attributed to charge transfer. The dependence of the (C60) m Cs3(-) anion yield on electron energy shows a resonance that, surprisingly, oscillates in strength as m increases from 1 to 6.

  6. Spatially resolved, substrate-induced rectification in C60 bilayers on copper

    DOE PAGES

    Smerdon, J. A.; Darancet, P.; Guest, J. R.

    2017-02-22

    Here, we demonstrate rectification ratios (RR) of ≳1000 at biases of 1.3 V in bilayers of C60 deposited on copper. Using scanning tunneling spectroscopy and first-principles calculations, we show that the strong coupling between C60 and the Cu(111) surface leads to the metallization of the bottom C60 layer, while the molecular orbitals of the top C60 are essentially unaffected. Due to this substrate-induced symmetry breaking and to a tunneling transport mechanism, the system behaves as a hole-blocking layer, with a spatial dependence of the onset voltage on intra-layer coordination. Together with previous observations of strong electron-blocking character of pentacene/C60 bilayersmore » on Cu(111), this work further demonstrates the potential of strongly hybridized, C60-coated electrodes to harness the electrical functionality of molecular components.« less

  7. 13C-NMR in Iodine and Potassium Intercalated C60 Solid

    NASA Astrophysics Data System (ADS)

    Maniwa, Yutaka; Shibata, Takayuki; Mizoguchi, Kenji; Kume, Kiyoshi; Kikuchi, Koichi; Ikemoto, Isao; Suzuki, Shinzo; Achiba, Yoji

    1992-07-01

    Iodine intercalated C60, I2.29C60, was studied by 13C NMR above 160 K. A sharp NMR signal and a strong temperature-dependent spin-lattice relaxation time, T1, indicated a presence of C60 molecular rotation much higher than 10 kHz at least down to 160 K. No evidence of metallic characteristics was found in the NMR shift (143± 1 ppm) and the T1 (40± 5 sec at room temperature). In K3C60, metallic behavior, T1T˜constant, was observed at the carbon sites between 20 K and 100 K. Electronic density of states at the Fermi level, N(EF), in I2.29C60 was estimated to be smaller than 0.12 of that in K3C60, assuming a relationship between N(EF) and T1T for normal metals.

  8. Uncontrolled variability in the extinction spectra of C60 nanoparticle suspensions.

    PubMed

    Chang, Xiaojun; Vikesland, Peter J

    2013-08-06

    To properly investigate the environmental transport, fate, and impact of fullerene C60 nanoparticles (nC60), it is necessary to reproducibly obtain nC60 suspensions and to accurately determine their concentration ([C60]). The results in the present study, however, clearly illustrate that the production of nC60 via extended mixing and via sonication are highly stochastic top-down processes subject to widely divergent end points. nC60 suspensions exhibit variable characteristics (e.g., [C60], average particle size, size distribution, etc.) that make it challenging, if not impossible, to acquire reproducible UV-vis extinction spectra. The mass extinction coefficient, which is the absorptivity of a suspension with [C60] = 1 mM obtained by normalizing UV-vis spectra by the mass concentration of C60 in the suspension, decreases with a given suspension's hydrodynamic diameter, whereas the particle extinction coefficient, which is the absorptivity of a suspension containing one mole of nC60 nanoparticles with the same size distribution as the target suspension and calculated based upon the suspension nanoparticle size distribution, increases with its number weighted average diameter. Other spectroscopic properties of nC60 (e.g., absorbance bandwidth, position of absorption maximum, and relative extinction intensity) also change with average particle size. As a result of the extant variability between samples, when UV-vis spectra are employed to calculate or represent [C60] for fullerene nanoparticle suspensions, extreme care must be taken and other colloidal properties of this suspension must be measured to obtain an accurate result.

  9. Study of the interaction of C60 fullerene with human serum albumin in aqueous solution

    SciTech Connect

    Li, Song; Zhao, Xiongce; Mo, Yiming; Cummings, Peter T; Heller, William T

    2013-01-01

    Concern about the toxicity of engineered nanoparticles, such as the prototypical nanomaterial C60 fullerene, continues to grow. While evidence continues to mount that C60 and its derivatives may pose health hazards, the specific molecular interactions of these particles with biological macromolecules require further investigation. To better understand the interaction of C60 with proteins, the protein human serum albumin (HSA) was studied in solution with C60 at C60:HSA molar ratios ranging from 1:2 to 4:1. HSA is the major protein component of blood plasma and plays a role in a variety of functions, such as the maintenance of blood pH and pressure. The C60-HSA interaction was probed by a combination of circular dichroism (CD) spectroscopy, small-angle neutron scattering (SANS) and atomistic molecular dynamics (MD) simulations to understand C60-driven changes in the structure of HSA in solution. The CD spectroscopy demonstrates that the secondary structure of the protein decreases in -helical content in response to the presence of C60. Similarly, C60 produces subtle changes in the solution conformation of HSA, as evidenced by the SANS data and MD. The data do not indicate that C60 is causing a change in the oligomerization state of the protein. Taken together results demonstrate that C60 interacts with HSA, but it does not strongly perturb the structure of the protein by unfolding it or inducing aggregation, suggesting a mechanism for transporting C60 throughout the body to accumulate in various tissues.

  10. Hybridization-Induced Carrier Localization at the C60/ZnO Interface

    SciTech Connect

    Kelly, Leah L.; Racke, David A.; Kim, Hyungchul; Ndione, Paul; Sigdel, Ajaya K.; Berry, Joseph J.; Graham, Samuel; Nordlund, Dennis; Monti, Oliver L. A.

    2016-05-25

    Electronic coupling and ground-state charge transfer at the C60/ZnO hybrid interface is shown to localize carriers in the C60 phase. This effect, revealed by resonant X-ray photoemission, arises from interfacial hybridization between C60 and ZnO. Such localization at carrier-selective electrodes and interlayers may lead to severely reduced carrier harvesting efficiencies and increased recombination rates in organic electronic devices.

  11. Low-temperature dynamics and spectroscopy in exohedral rare-gas C60 fullerene complexes

    NASA Astrophysics Data System (ADS)

    Ruiz, A.; Hernández-Rojas, J.; Bretón, J.; Gomez Llorente, J. M.

    2001-03-01

    The adatom dynamics in exohedral C60 fullerene complexes of rare-gas atoms are studied with a three degrees of freedom model. The eigenvalue problem of the corresponding quantum Hamiltonian is solved and the electric-dipole spectra for ArC60, NeC60, and HeC60 in the low-temperature range from 5 to 40 K are simulated. The most important spectral features are related to the degree of angular anisotropy in the adatom-C60 interaction. The ArC60 and NeC60 complexes present very simple spectra which can be assigned in terms of three-mode oscillators; the corresponding motion takes place in the deep hexagon wells (also in the pentagon wells for NeC60) of the interaction potential. On the contrary, the HeC60 complex shows more complicated spectra with important tunneling effects due to the smaller angular anisotropy of the interaction. The onset of almost free internal rotation takes place in this complex at rather low energies, and this gives rise to a low-frequency rotational band in the spectra at temperatures above T˜15 K.

  12. Rock-salt-type crystal of thermally contracted C60 with encapsulated lithium cation.

    PubMed

    Aoyagi, Shinobu; Sado, Yuki; Nishibori, Eiji; Sawa, Hiroshi; Okada, Hiroshi; Tobita, Hiromi; Kasama, Yasuhiko; Kitaura, Ryo; Shinohara, Hisanori

    2012-04-02

    Rock solid: fullerene-encapsulated Li(+) (Li(+)@C(60)) is an alkaline cation owing to the spherical shape and positive charge. Li(+)@C(60) crystallizes as a rock-salt-type crystal in the presence of PF(6)(-). The orientations of C(60) and PF(6)(-) (orange) are perfectly ordered below 370 K, and Li(+) (purple) hops within the cage. At temperatures below 100 K two Li(+) units are localized at two polar positions within each C(60) . Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Escherichia coli Inactivation by UVC-Irradiated C60: kinetics and mechanisms.

    PubMed

    Cho, Min; Snow, Samuel D; Hughes, Joseph B; Kim, Jae-Hong

    2011-11-15

    Motivated by recent studies that documented changes in fullerene toxicity after chemical transformation, C(60) aggregates (nC(60)) were subject to UVC irradiation at monochromatic 254 nm and subsequently evaluated for antibacterial and bactericidal properties against Escherichia coli. The nC(60) treated with UVC irradiation, referred to herein as UVC-irradiated C(60), did not directly inhibit bacterial growth at concentrations up to 20 mg/L. In the presence of UVA and visible light, however, UVC-irradiated C(60) rapidly inactivated E. coli, suggesting that photochemical production of reactive oxygen species (ROS) was involved. The use of ROS scavengers and probes determined that hydroxyl radicals were the primary ROS responsible for the E. coli inactivation. Results from protein release, lipid peroxidation, cell permeability, and intracellular enzyme assays sugge