Effect of oxygen on the electrophysical properties of some carbon allotropes (graphite and C60 fullerene)

The electrophysical properties of powder samples of graphite and C₆₀ fullerene have been studied in vacuum, oxygen ambient, and air. Room-temperature conduction of the samples has a percolative character. An increase of temperature brings about an increase of sample conductivity caused by oxygen desorption from the bulk. A peak-shaped feature not observed before has been found in the temperature behavior of the resistance of finely dispersed C₆₀ and graphite powder samples in the T=310–340 K interval. Oxygen atoms were found to be involved in charge transport in powder samples of graphite and C₆₀ fullerene through their electrical activity on the surface of grains differing in size. Fiz. Tverd. Tela (St. Petersburg) 39, 1703–1705 (September 1997)     

Electron-induced radiation from C60 fullerene in the gas phase

The formation of radiating particles in the excitation of C₆₀ fullerene molecules by electrons with energies E _e<100 eV is investigated by the method of crossed molecular and electron beams. A quasicontinuous (with a spectral resolution of 3 nm) emission spectrum, close to the Planck emission spectrum of a heated body, is recorded in the wavelength range 300–800 nm. The temperature of the radiation corresponds to an internal energy of the C₆₀ molecule of approximately 40 eV. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 12, 915–919 (25 June 1996)     

Electronic and optical properties of fullerene nanostructures

Two new types of molecular/electronic fullerene nanostructures are considered: 1) highly stable hydrated clusters (I _h symmetry group) and microcrystals (T _h symmetry group) of fullerene C₆₀ in water solution and 2) the single-walled carbon nanotube from C₆₀ fullerenes. The vibrational spectra of these fullerene nanostructures are calculated using molecular dynamics. The electronic properties of a single-walled fullerene nanotube are investigated using the tight-binding method. The theoretical results obtained were compared with available experimental data. Fiz. Tverd. Tela (St. Petersburg) 41, 885–887 (May 1999) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor.     

Electronic structure of linear chains of fullerenes

The band structure of linear chains of fullerene molecules is calculated as a function of the intermolecular π-electron overlap integral T, which increases under increasing external pressure. Chains consisting of neutral (C₆₀) and charged (C ₆₀ ⁻ ) molecules are studied. It is shown that there is a sharp transition from a metal (or narrow-gap semiconductor) to an insulator (with band gap ∼1 eV)with increasing T. The proposed model makes it possible to describe the formation of solid-carbon struc-tures, containing chains of covalently bound fullerene molecules, with different pressure-dependent semiconductor properties. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 8, 647–650 (25 April 1997)     

C<Subscript>60</Subscript> fullerene as an η<Superscript>6</Superscript> ligand in π complexes of transition metals

The possible existence of complexes formed by the C₆₀ fullerene or its derivatives with transition metals interacting with the carbon cage via η⁶−π type bonding is discussed. The derivatives C₆₀ R ₆ of the C₆₀ fullerene (R = −, H, F, Cl, Br, CN) are analyzed using the density functional method within the Perdew-Burke-Ernzerhof approximation. In these molecules, the R groups are attached to carbon atoms located in the α positions with respect to the common hexagon of the C₆₀ fullerene. The structure and electron configuration of complexes formed by these molecules with Cr(C₆H₆), Cr(CO)₃, MoC₆H₆, and Mo(CO)₃ particles are modeled. The “dimer” systems C₆₀R₆-M-R ₆C₆₀ (M = Cr, Mo, R =-, H, F) are investigated in which two fullerene molecules interact via a transition-metal atom. It is found that the introduction of six R groups in the α sites with respect to the common hexagon of C₆₀ favors the formation of complexes of these derivatives of the C₆₀ fullerene with the Cr(C₆H₆), Cr(CO), Mo(C₆H₆), and Mo(CO)₃ particles in which η⁶-π type bonds arise between the metal and the atoms of the hexagon fringed with the R groups. It is also demonstrated that analogous complexes with a “bare” C₆₀ fullerene are possible, but they are significantly less stable. The (C₆H₆) M-R ₆C₆₀ R ₆-M (C₆H₆) complexes of particles M(C₆H₆) (M= Cr, Mo) and derivatives R ₆C₆₀ R ₆ (R =-, H, F, Cl, Br) are studied. In the R ₆C₆₀ R ₆ molecule, six R groups are located in the α sites with respect to the common hexagon of the C₆₀ fullerene and six other groups fringe the opposite hexagon. The obtained results can be applied to planning synthesis of new complexes that C₆₀ fullerene derivatives can form with transition metals. Original Russian Text ￠ E.G. Gal’pern, A.R. Sabirov, I.V. Stankevich, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 12, pp. 2220–2223.     

Electronic structure of graphite nanopipes

A recursion method is used for calculating the electron-state density n(E) of carbon in diamond, graphite, C₆₀ fullerene, and graphite nanopipes of various structures and diameters. The calculated n(E) for diamond, graphite, and fullerene are compared with experimental data. The distinctive features of the electron-state density n(E) in graphite nanopipes are discussed. Fiz. Tverd. Tela (St. Petersburg) 39, 1118–1121 (June 1997)     

Temperature dependence of the spin-lattice relaxation time in local triplet-excited states of a doped C60 fullerene crystal

The temperature dependence of the spin-lattice relaxation time of triplet-excited impurity centers of a C₆₀ fullerene crystal is investigated within the framework of the spin-phonon coupling mechanism which arises as a result of the admixture of rotational to translational motions of the molecules due to acoustic lattice vibrations. General expressions are obtained for the transition probabilities for the direct single-phonon and Raman two-phonon processes. The method of atom-atom potentials is used to carry out a concrete calculation of the spin-lattice relaxation time for an isotopic impurity in a C₆₀ crystal. Fiz. Tverd. Tela (St. Petersburg) 39, 1699–1702 (September 1997)     

Novel Nanocomposites of Polypyrrole Doped with Fullerene C60

This paper reports on the structural, thermal, and dielectric properties of polypyrrole/fullerene C₆₀ nanocomposites synthesized by a interfacial polymerization method. Fourier transform infrared (FT-IR) and ultraviolet-visible (UV-vis) analyses clearly indicated the existence of interactions between polypyrrole (PPy) and the fullerene C₆₀ nanoparticles. Thermal analyses indicated that the extrapolated onset degradation temperature (T_deg) of PPy increased with increasing doping level. Scanning electron microscopy (SEM) images showed that the fullerene C₆₀ changed the morphology of PPy. Dielectric analyses showed a temperature dependent dielectric relaxation behavior. The relaxation time of the nanocomposites with high doping levels tended to increase with increasing temperature. This behavior of the polypyrrole/fullerene C₆₀ nanocomposites indicated that they could be used as a high temperature ultrasonic transducer.     

Electronic properties of C60 single crystals doped with lithium by electrodiffusion

Diffusion of lithium cations in C₆₀ single crystals driven by electric field has been detected and studied. A novel technique for fullerene crystal doping based on injection of ions through a “superionic crystal/C₆₀ single crystal” heterojunction has been suggested. It has been found that lithium doping of C₆₀ single crystals brings about an ESR signal, and this signal as a function of time has been investigated. The electronic conductivity in Li_xC₆₀ crystals has a nonmetallic nature. Reflection spectra measured in the IR band have shown that the reflectivity due to free electrons gradually decreases with time, which correlates with the evolution of signals due to ESR and microwave conductivity. Lithium doping of crystals increases the oscillator strength of the T _1u (4) vibrational mode and shifts it to lower frequencies (from 1429 cm⁻¹ to 1413 cm⁻¹), which indicates that one electron is present at the C₆₀ molecule, and this fact may be treated as evidence that the LiC₆₀ phase is generated in a C₆₀ crystal. Zh. éksp. Teor. Fiz. 116, 1706–1722 (November 1999)     

C60 fullerite with a “stretched” fcc lattice

It is shown that deuteration of C₆₀ fullerite followed by thermal decomposition of the resulting deuteride C₆₀D₂₄ leads to the formation of an fcc lattice with a ₀=14.52 Å in the final product, which according to the IR spectra consists mainly of C₆₀ fullerene molecules. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 3, 239–242 (10 August 1998)     

Effect of low-temperature compression on the parameters of the phase transition at 250–260 K in C60 single crystals

A thermodynamic transition in C₆₀ crystals, subjected beforehand to uniaxial compression at various temperatures and to thermal action, was investigated by differential scanning calorimetry. It was established that compression of the crystal at temperatures below the phase transition has a much smaller effect on the transition itself than a similar or even much weaker action at a temperature above the phase transition. A “quenching” effect was also found. This effect is probably due to the orientational order of individual fullerene molecules. A correlation was established between the magnitude of the effect and the preliminary deformation of C₆₀ crystals. Fiz. Tverd. Tela (St. Petersburg) 41, 550–553 (March 1999)     

Calorimetric studies of C70S48 crystals

A comparative study of the thermodynamic properties of the C₇₀ fullerene, sulfur, and C₇₀S₄₈ crystals has been made by differential scanning calorimetry. It is shown that only C₇₀S₄₈ has an endothermic δ phase transition with a peak at 430 K, which lies in the temperature region exhibiting conductivity and dielectric anomalies. A correlation between the behavior of the sulfur sublattice in the C₇₀S₄₈ crystals and the thermodynamic parameters of the transition has been established. Fiz. Tverd. Tela (St. Petersburg) 41, 360–363 (February 1999)     

Interaction of C60 molecules with a (100) Mo surface

The adsorption, initial stages of film growth, and transformation of an adlayer of C₆₀ molecules on a (100) Mo surface upon heating are studied under ultrahigh-vacuum conditions. It is shown that the C₆₀ molecules remain intact in the adsorbed state up to 760 K. Layer-by-layer growth of a fullerite film is observed at room temperature, while tower-shaped crystallites grow up from a loosely packed monolayer with an approximate concentration of C₆₀ molecules equal to (1.3±0.2)×10¹⁴ molecules · cm⁻² at 500–600 K. In the latter case the percentage of the surface occupied by them depends on the temperature and the impinging flux density of fullerene molecules, but after a certain stationary value has been achieved, it scarcely depends on the exposure time. Zh. Tekh. Fiz. 69, 117–122 (November 1999)     

Crystalline complexes of fullerene with anisole derivatives

For the first time, bis(anisole)chromium fulleride (PhOMe)₂Cr^+·[C₆₀]^−· and a crystalline complex of fullerene with ortho-butoxyanisole have been obtained. The temperature dependence of the parameters of the EPR spectrum of bis(anisole)chromium fulleride (PhOMe)₂Cr^+·[C₆₀]^−· has been studied. The molecular structure of the complex of fullerene with ortho-butoxyanisole has been established.     

IR photoconductivity of C60 fullerene single crystals

The photoconductivity in the range 0.3–0.9 eV was investigated in a high-quality C₆₀ fullerene single crystal. It was concluded that the crystal investigated is an extrinsic semiconductor. Fiz. Tverd. Tela (St. Petersburg) 41, 1113–1114 (June 1999)     

Synthesis and photophysical properties of polyamides containing in-chain porphyrin and [60]fullerene

Conjugated polyamides containing porphyrin and [60]fullerene (C₆₀) in the main chain were prepared by a direct polycondensation of the 3′H,3″H-dicyclopropa[1, 9:16, 17] [5, 6]fullerene-C₆₀-I _h -3′,3″-dicarboxylic acid and 5,15-bis(4-aminophenyl)-10,20-bis(3,5-dialkoxyphenyl)porphyrin in the presence of triphenyl phosphite and pyridine. Gel permeation chromatography (GPC) analysis of the polyamides showed the weight-average molecular weight was about 23,626–23,736, and the temperature at 5% weight loss determined by thermogravimetric analysis (TGA) was above 216 °C. The transmission electron microscopy (TEM) images displayed the regular one-dimensional linear arrays of the polyamides with lengths exceeded 200 nm. The photoinduced electron transfer from porphyrin to C₆₀ in the polyamides was observed in nanosecond laser-flash photolysis experiments at ambient temperature, which produced a charge-separated state (porphyrin radical cation–C₆₀ radical anion pair) with a lifetime as long as 40 μs. The calculated ratio of k _CS/k _CR was found to be 2.1 × 10⁴. They could have potential applications for photoelectronic devices, organic solar cells and so on.     

Anomalous Ortho-to-Para Ratio of Nuclear Spin Isomers of H2O at Low Temperatures

A theoretical model proposed for nuclear spin isomers of H₂O molecules located inside the C₆₀ fullerene explains an anomalously high stability of ortho-H₂O isomers detected in the experiments reported in [B. Meier et al., Nature Commun. 6, 8112 (2015)] at a temperature of T = 5 K.

     

Anomalous magnetic properties of the complex (ET)2C60

Investigations of the temperature dependences of the magnetic permeability and dielectric permittivity in the temperature range 4.2 K⩽T ⩽300 K and the field dependence of the magnetization M(B) in fields B⩽50 T show that the magnetic properties of the complex (ET)₂C₆₀ cannot be described on the basis of the standard model, which assumes that the paramagnetic oxygen impurity makes the dominant contribution. It is found that the magnetism in (ET)₂C₆₀ is due to the diamagnetic properties of the C₆₀ and ET molecules and to specific paramagnetic centers of the type C ₆₀ ⁻ , which possess an anomalously low g factor |g|≈0.14. An experimentum crucis is proposed for checking the oxygen paramagnetic center model for pure C₆₀ films. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 10, 733–738 (25 May 1999)     

Cycloaddition of 2′-azidoethyl glycosides to fullerene[C60] under ultrasonic irradiation

The reactions of fullerene[C₆₀] with 2′-azidoethyl 2,3,4,6-tetra-O-acetyl-α-d-mannopyranoside (2a) and 2′-azidoethyl 2,3,4,6-tetra-O-acetyl-β-d-galactopyranoside (2b) under ultrasonic irradiation cause the cycloaddition of 2′-azidoethyl glycosides to fullerene[C₆₀] and lead to d-glycosyl fullerene[C₆₀] derivatives 3a and 3b, respectively. The glycosyl fullerene[C₆₀] derivatives were characterized by ¹H and ¹³C NMR, UV–vis, FAB-MS, FT-IR spectra and were a 1:1 glycoside fullerene [C₆₀]-adduct.     

Thermal expansion of thin C60 films

The thermal expansion coefficient a and structure of C₆₀ films with thickness t∼3–10 nm were investigated in the temperature interval from room to liquid-nitrogen temperature by electron-optical methods. The thermal expansion coefficient was determined from the temperature shift of the diffraction maxima in the electron diffraction patterns. The objects of investigation were epitaxial C₆₀ films condensed in vacuum on a (100) NaCl cleavage surface and oriented in the (111) plane. A surface-induced size effect in the thermal expansion coefficient was observed. It was established that as t decreases α _f increases and is described well by the relation α _f=17·10⁻⁶ K⁻¹+8.3·10⁻⁵ nm K⁻¹ t ⁻¹. This relation was used to estimate the linear expansion coefficient α _s of the C₆₀ surface in the (111) plane as α _s=60·10⁻⁶K⁻¹, which is several times larger than the bulk value. The experimental results agree satisfactorily with the theoretical calculations of the mean-square displacements of molecules located in a region near the surface. Zh. éksp. Teor. Fiz. 114, 1868–1875 (November 1998)