New property of the fullerenes: the anomalously effective quenching of electronically excited states owing to energy transfer to the C<Subscript>70</Subscript> and C<Subscript>60</Subscript> molecules

The quenching of the electronically excited states of various energy donors—Tb³⁺; 9,10-anthracene dibromide; and adamantanone—by C₇₀ fullerene has been detected and analyzed. The quenching is characterized by anomalously high biomolecular quenching rate constants, which are obtained from the Stern-Volmer dependences of the energy-donor photoluminescence intensity on the concentration of the C₇₀ molecules. It has been shown that the high efficiency of quenching by the C₇₀ fullerene as compared to the C₆₀ fullerene is due to the higher polarizability of the C₇₀ molecule and large overlap integrals of the energy-donor photoluminescence spectra with the absorption spectrum of the C₇₀ fullerene.     

Phase Transitions in a Mixture of Amorphous C<Subscript>60</Subscript> and C<Subscript>70</Subscript> Fullerene Phases at High Temperatures and Pressures

Phase transitions in two types of amorphous fullerene phases (C₆₀–C₇₀ (50/50) mixtures and an amorpous C₇₀ fullerene phase) are studied via neutron diffraction at pressures of 2–8 GPa and temperatures of 200–1100°C. Fullerenes are amorphized by grinding in a ball mill and sintered under quasi-hydrostatic pressure in a toroidal-type chamber. Diffraction studies are performed ex situ. It is shown that the amorphous phase of fullerenes retains its structure at temperatures of 200–500°C, and amorphous graphite is formed at 800–1100°C with a subsequent transition to crystalline graphite. This process is slow in a mixture of fullerenes, compared to C₇₀ fullerene. According to neutron diffraction data, the amorphous graphite formed from amorphous fullerene phases has anisotropy that is much weaker in a fullerene mixture.     

Thermally stimulated desorption of C<Subscript>60</Subscript> and C<Subscript>70</Subscript> fullerenes from rigid-chain polyimide films

Polyimide-fullerene composite thin coatings are investigated using thermal desorption mass spectrometry in the temperature range 20–800°C. It is found that, at temperatures below the temperature of decom-position of the polymer matrix, thermally stimulated desorption of fullerene molecules is limited by the diffusion of fullerene molecules in the matrix. The diffusion coefficients and activation energies of diffusion of C₆₀ and C₇₀ fullerene molecules are determined from the experimental data on thermally stimulated desorption in the framework of several approaches. It is revealed that the diffusion of C₇₀ molecules in the polyimide matrix is more hindered than the diffusion of C₆₀ molecules in the same matrix.     

Withdrawal of Electrodynamical Forbiddance and Peculiarities of the SERS Spectra in Fullerene C<Subscript>70</Subscript>

It is demonstrated that in fullerene C₇₀, which can be considered as a deformed fullerene C₆₀ in some mean sense there is a withdrawal of an Electrodynamical forbiddance of a strong quadrupole light-molecule interaction, which is realized in the fullerene C₆₀. This situation occurs because of the reduction of symmetry of C₆₀ from the icosahedral symmetry group Y_h to the group D_5h. The withdrawal results in appearance of the lines in the SERS spectra of C₆₀, which are forbidden in usual Raman scattering and are active in the infrared absorption spectra. The experimentally measured SERS spectra of C₇₀ demonstrates existence of such lines that strongly confirms our ideas about the dipole-quadrupole SERS mechanism.     

Effect of heating of the electronic subsystem on the thermal stability of the C<Subscript>60</Subscript> and C<Subscript>20</Subscript> fullerenes and (C<Subscript>20</Subscript>)<Subscript>2</Subscript> cluster molecule

The effect of heating of the electronic subsystem on the thermal stability of C₆₀ and C₂₀ fullerenes and a (C₂₀)₂ cluster molecule is investigated theoretically. It is demonstrated that the excitation of electrons to upper energy levels in accordance with the Fermi-Dirac distribution function does not lead to a substantial change in the activation energy E _a for decay of the C₂₀ fullerene. The stability of the C₆₀ fullerene and the (C₂₀)₂ cluster molecule likewise does not change radically. However, the inclusion of corrections associated with the finite sizes of the heat bath leads to the activation energy E _a which is in better agreement with the calculated height of the potential barrier preventing the cluster decay.     

Collision dynamics of He@C<Subscript>60</Subscript>+He@C<Subscript>60</Subscript> at low energies

A semi-empirical molecular dynamics model is developed. The central collisions of C₆₀+C₆₀ and He@C₆₀+He@C₆₀ at different incident energies are investigated based on this model. It is found that the dimer structures have been produced at proper incident energies and these fullerene dimers could be formed by a self-assembly of C₆₀ fullerene and He@C₆₀. The He atom has a significant effect at higher incident energy and this embedded He atom can enhance the stability of the dimer structure.     

Impact of a physiological medium on the aggregation state of C<Subscript>60</Subscript> and C<Subscript>70</Subscript> fullerenes

The C₆₀ and C₇₀ fullerene-cluster size distribution in aqueous solutions and a physiological medium is studied via dynamic light scattering. The initial aqueous solutions of fullerenes obtained via different methods are found to contain clusters with a characteristic size of about 100 nm. The additional aggregation of fullerenes is observed after their transfer into a physiological medium (0.9% NaCl) and is established to depend on the preparation method. The cluster-size distribution in a fullerene–pectic-acid mixture is found to vary in water and a physiological medium. The results reveal the need for additional studies of the structure and properties of C₆₀ and C₇₀ molecules, as well as their complexes with medicines, in a physiological medium for medical applications.     

Vibrational spectra of 2-cyclooctylamino-5-nitropyridine and its mixtures with C<Subscript>60</Subscript> and C<Subscript>70</Subscript> fullerenes

The vibrational spectra of 2-cyclooctylamino-5-nitropyridine (COANP) solutions and the evolution of the spectra upon changing over from the solutions to solid-phase COANP are investigated. The bands observed in the spectra are assigned to the corresponding vibrational modes. The nature of the interaction of COANP with C₆₀ and C₇₀ fullerenes is elucidated by analyzing the transmission spectra of these compounds. No interaction of the COANP compound with C₆₀ and C₇₀ fullerenes is revealed under the studied conditions. It is assumed that the physical nature of this phenomenon can be associated with the formation of liquid-crystal clusters consisting of fullerene molecules.     

The oxidation of fullerenes (C<Subscript>60</Subscript>, C<Subscript>70</Subscript>) with various oxidants under ultrasonication

The reaction of C₆₀, under ultrasonication, with various oxidants, such as 3-chloroperoxy benzoic acid (Fluka 99%), 4-methyl morpholine N-oxide (Aldrich 97%), chromium (VI) oxide (Aldrich 99.9%), and the oxone® monopersulfate compound, causes the oxidation of fullerenes at room temperature. The FAB-MS spectra and HPLC profile confirmed that the products of fullerene oxidation were [C₆₀(O)_n] (n=1～3 or n=1). C₇₀ also reacted, under ultrasonication, with various oxidants, but the reaction rate of C₇₀ was lower than that of C₆₀.     

Rotation of the inner shell in a C<Subscript>20</Subscript>@C<Subscript>80</Subscript> nanoparticle

The stability of a C₂₀@C₈₀ nanoparticle and the rotation of its inner shell are studied theoretically within the tight-binding approximation. It is found that the C₂₀ skeleton in the free state is described by space group D_3d; in the case where C₂₀ is placed into the C₈₀(I _h ) fullerene field, the space group of C₂₀ is raised to I _h due to isomerization. The total energy surface of the C₂₀@C₈₀ compound is scanned over two rotation angles. Based on an analysis of the surface relief and energy isoline map, orientational melting of the nanoparticle is predicted. A nanoparticle gyroscope—C₂₀ rotating in the field of C₈₀ at a certain relative orientation and energy supply—is also predicted to exist.     

Anomalous thermal stability of metastable C<Subscript>20</Subscript> fullerene

The results of computer simulation of the dynamics of fullerene C₂₀ at different temperatures are presented. It is shown that, although it is metastable, this isomer is very stable with respect to the transition to a lower energy configuration and retains its chemical structure under heating to very high temperatures, T ≈ 3000 K. Its decay activation energy is found to be E _a ≈ 7 eV. Possible decay channels are studied, and the height of the minimum potential barrier to decay is determined to be U = 5.0 eV. The results obtained make it possible to understand the reasons for the anomalous stability of fullerene C₂₀ under normal conditions.     

Molecular dynamics simulation of the low-energy interaction between Cu<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>@C<Subscript>60</Subscript> endofullerenes and the surface of a copper crystal

A molecular dynamics simulation of the low-energy interaction of C₆₀ fullerenes and Cu₁@C₆₀, Cu₆@C₆₀, and Cu₁₃@C₆₀ endofullerenes with a Cu(100) surface was performed. The effects of a copper cluster encapsulated in a fullerene and of a fullerene’s translational motion and rotation energy on its penetration into a surface were investigated. It was shown that the presence of an encapsulated cluster has a positive effect on fullerene penetration into a surface with preservation of the fullerene’s structure. The optimal conditions for fullerene penetration into a copper crystal surface were determined.     

Low energy electron attachment to C<Subscript>60</Subscript>

Low energy electron attachment to the fullerene molecule (C₆₀) and its temperature dependence are studied in a crossed electron beam–molecular beam experiment. We observe the strongest relative signal of C₆₀ anion near 0 eV electron energy with respect to higher energy resonant peaks confirming the contribution of s-wave capture to the electron attachment process and hence the absence of threshold behavior or activation barrier near zero electron energy. While we find no temperature dependence for the cross-section near zero energy, we observe a reduction in the cross-sections at higher electron energies as the temperature is increased, indicating a decrease in lifetime of the resonances at higher energies with increase in temperature.     

Modeling of the structure and electronic structure of condensed phases of small fullerenes C<Subscript>28</Subscript> and Zn@C<Subscript>28</Subscript>

A comparative analysis of the stability factors and electronic structure of two possible crystalline forms of small fullerene C₂₈ and endohedral fullerene Zn@C₂₈ with diamond and lonsdaleite structures is performed using a cluster model. Atoms of elements that, when placed inside C₂₈ cages, have no significant effect on the stability of free small-fullerene molecules are shown to be able to dramatically change the electronic properties and reactivity of the C₂₈ skeleton and to be favorable for forming small-fullerene crystalline modifications, which are covalent crystals. In contrast, if the presence of foreign atoms inside C₂₈ cages stabilizes the isolated nanoparticles, then molecular crystals (such as C₆₀ fullerites) are formed due to weak van der Waals forces.     

Tuning the electronic properties of the fullerene C<Subscript>20</Subscript> cage via silicon impurities

The fullerene C₂₀ represents one of the most active classes of nanostructures, and they have been widely used as active materials for important applications. In this study, we investigate and discuss the tuning of the electronic properties of the fullerene C₂₀ cage via various consternations and locations of silicon atoms. All calculations are based on the density functional theory (DFT) at the B3LYP/3-21G level through the Gaussian 09W program package. The optimized structures, density of state (DOS) analysis, total energies, dipole moments, HOMO energies, Fermi level energies, LUMO energies, energy gaps, and the work functions were performed and discussed. Our results show that the electronic properties of C₂₀ cage do not only depend on the silicon impurity concentrations, but also depend on the geometrical pattern of silicon impurities in the C₂₀ cage. The tuning of the electronic properties leads to significant changes in the charge transport and the absorption spectra for C₂₀ cage via engineering the energy gap. So, we suggest that substitutional impurities are the best viable option for enhancement of desired electronic properties of C₂₀ cage for using these structures in nanoelectronics and solar cell applications.     

Study of the Initial Stage of Fluorinated C<Subscript>60</Subscript>F<Subscript>18</Subscript> Fullerene Adsorption on the Cu(001) Surface

The dynamics of the adsorption and evolution of fluorinated C₆₀F₁₈ fullerene molecules on the Cu(001) surface are studied by real-time ultra-high vacuum scanning tunneling microscopy. Fluorinated fullerene molecules are shown to decompose with time on the Cu(001) surface transforming to C₆₀ molecules. The decay rate depends on the initial molecular coverage. The rapid decay of fluorinated fullerene molecules is observed when the coverage is no higher than 0.2 single layers. As a result, two-dimensional islands consisting of pure C₆₀ molecules are formed on the Cu(001) surface. 2D islands consisting of fluorinated fullerene molecules are formed when the initial molecular coverage is higher than 0.5 single layers. The molecules inside these islands also tend to decompose with time. It is found experimentally that fluorine atoms are removed completely from the initial C₆₀F₁₈ molecules adsorbed on the Cu(001) surface after 250 h when the initial molecular coverage is 0.6 single layers.     

Electron transmission and quantum current distribution of C<Subscript>70</Subscript> molecule

The characteristics of electron transmission through C₇₀ molecule bridge in which two atomic chain leads are connected to long-axis carbon atoms are investigated theoretically by using tight-binding approach based on the Green’s function with only one π orbital electron per carbon atom. Electron transmission through C₇₀ molecule from the input to the output terminal is obtained. From the spectrum, the switching feature of the electron transmission through C₇₀ is found, and the oscillation property based on the quantized level is explained. The quantum current distributions inside C₇₀ molecule bridge are calculated and simulated by the quantum current density theory based on Fisher-Lee formula at the energy point E = −0.2 eV, where the transmission spectrum shows a peak. The maximum and the minimum bond quantum currents are presented, and the reason why the currents are distributed nonuniformly is explained by the phase difference of the atomic orbits. The result shows that the currents at each atomic site agree with Kirchhoff quantum current conservation law. Supported by the National Key Basic Research Development Project (Grant No. 2003CB716204), the International Corporation Project of the Education Department of China (Grant No. 20050360563), the Key Laboratory of Advanced Photonic and Electronic Materials of Jiangsu (Grant No. BM2003202) and the State Key Laboratory of Solid State Microstructures of Nanjing University     

Photoinduced optical activity of C<Subscript>70</Subscript> fullerene in organic solvents

We have experimentally studied for the first time the effect of photoinduced rotation of the plane of polarization for pulsed laser radiation in solutions of C₇₀ fullerene in organic solvents and their mixtures. We have shown that the effect is observed for elliptical polarization of the laser radiation and is absent for linear polarization. We present the results of a study of the nonlinear optical characteristics of the C₇₀ solutions. We discuss the physical mechanisms by which nonlinear gyrotropy is induced in solutions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 93–99, January–February, 2009.     

Nonlinear transmission of the liquid crystal-polyaniline-C<Subscript>60</Subscript> system in the near-infrared range

The nonlinear transmission of the liquid crystal-conductive polymer (polyaniline)-fullerence (C₆₀) system in the near-infrared spectral region at 1080 and 805 nm is considered for the first time. The output radiation intensity is studied as a function of the fullerence concentration and the energy density of the incident radiation in the nano- and femtosecond scales. The experimental results are explained by the formation of an organic donor-fullerene complex, as well as by possible absorption of fullerence C₆₀ at the 1 6-eV transition, which is forbidden in pure fullerene structures.     

High-pressure hydrogenated fullerenes: Optical spectra and stability of C<Subscript>60</Subscript>H<Subscript>36</Subscript> at high pressure

The optical Raman and photoluminescence (PL) spectra of the high-pressure hydrogenated fullerene C₆₀ are studied at normal conditions and at high pressure. The Raman spectrum of the most stable hydrofullerene C₆₀H₃₆ contains a large number of peaks related to various isomers of this molecule. Comparison of the experimental data with the results of calculations shows that the most abundant isomers have the symmetries S₆, T, and D_3d. The Raman spectrum of deuterofullerene C₆₀H₃₆ is similar to that of C₆₀H₃₆, but the frequencies of the C-H stretching and bending modes are shifted due to the isotopic effect. The PL spectrum of hydrofullerene C₆₀H₃₆ is shifted to higher energies by approximately 1 eV with respect to that of pristine C₆₀. The effect of hydrostatic pressure on the Raman and PL spectra of C₆₀H₃₆ has been investigated up to 12 GPa. The pressure dependence of the phonon frequencies exhibits peculiarities at approximately 0.6 and 6 GPa. The changes observed at approximately 0.6 GPa are probably related to a phase transition from the initial orientationally disordered body-centered cubic structure to an orientationally ordered structure. The peculiarity at approximately 6 GPa may be related to a pressure-driven enhancement of the C-H interaction between the hydrogen and carbon atoms belonging to neighboring molecular cages. The pressure-induced shift of the photoluminescence spectrum of C₆₀H₃₆ is very small up to 6 GPa, and a negative pressure shift was observed at higher pressure. All the observed pressure effects are reversible with pressure.