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)     

Regularity criteria for linear chains

The structural analysis of linear chains of arbitrary fixed shape is discussed in the context of a spectral approach. The shape of the chain is characterized by a set of scalar and pseudoscalar invariants, which remain constant under translations and rotations. The statistical properties of the set of invariants are compared with the analogous characteristics for a freely linked chain. The proposed criteria have the self-averaging property for relatively short (∼100–300 links) chains and can be used to discern possible latent periodicities and symmetries in a system. As examples, two applications of the theory are considered: the structural analysis of chains generated by random walks on a cubic lattice and protein C_α backbones. Zh. éksp. Teor. Fiz. 116, 620–635 (August 1999)     

Mechanism of the formation of a diamond nanocomposite during transformations of C60 fullerite at high pressure

The results of an investigation of the transformation of C₆₀ fullerite to diamond under pressure through intermediate three-dimensionally polymerized and amorphous phases are reported. It is found that treatment of fullerite C₆₀ at pressures 12–14 GPa and temperatures ∼1400°C produces a nanocrystalline graphite-diamond composite with a concentration of the diamond component exceeding 50%. At lower temperatures (700–1200°C) nanocomposites consisting of diamondlike (sp ³) and graphitic (sp ²) amorphous phases are formed. The nanocomposites obtained have extremely high mechanical characteristics: hardness comparable to that of best diamond single crystals and fracture resistance two times greater than that of diamond. Mechanisms leading to the transformation of C₆₀ fullerite into diamond-based nanocomposites and the reasons for the high mechanical characteristics of these nanocomposites are discussed. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 11, 822–827 (10 June 1999)     

Collective effects accompanying magnetization of two-dimensional lattices of nanosize magnetic particles

Collective effects arising in a two-dimensional lattice of nanosize magnetic particles as a result of the dipole interparticle interaction are investigated by Hall magnetometry. The experimental system consists of 10⁵ permalloy particles having a diameter of ∼40 nm and a height of ∼40 nm and forming a lattice with a rectangular unit cell (90 nm×180 nm). We attribute the characteristic features observed in the magnetization curves to quasi-one-dimensionality of the experimental lattice of particles and to the formation of solitons in chains of dipoles. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 6, 475–479 (25 September 1998)     

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)     

Thermal conductivity of crystalline fullerite C60 in the simple cubic phase

The behavior of the thermal conductivity k(T) of bulk faceted fullerite C₆₀ crystals is investigated at temperatures T=8–220 K. The samples are prepared by the gas-transport method from pure C₆₀, containing less than 0.01% impurities. It is found that as the temperature decreases, the thermal conductivity of the crystal increases, reaches a maximum at T=15–20 K, and drops by a factor of ∼2, proportional to the change in the specific heat, on cooling to 8 K. The effective phonon mean free path λ _p, estimated from the thermal conductivity and known from the published values of the specific heat of fullerite, is comparable to the lattice constant of the crystal λ _p∼d=1.4 nm at temperatures T>200 K and reaches values λ_p∼50d at T<15 K, i.e., the maximum phonon ranges are limited by scattering on defects in the volume of the sample in the simple cubic phase. In the range T=25−75 K the observed temperature dependence k(T) can be described by the expression k(T)∼exp(Θ/bT), characteristic for the behavior of the thermal conductivity of perfect nonconducting crystals at temperatures below the Debye temperature Θ (Θ=80 K in fullerite), where umklapp phonon-phonon scattering processes predominate in the volume of the sample. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 8, 651–656 (25 April 1997)     

Polarons in linear chains of fullerenes

Polaron states in linear chains of fullerenes are studied with the use of the generalized model of Su-Shrieffer-Heeger (SSH) for the intermolecular and intramolecular degrees of freedom. Electron charge distributions over the molecular surface and Jahn-Teller distortions of carbon atoms in C₆₀ are calculated self-consistently for linear C₆₀ polymer and C ₆₀ ⁻ polyanion chains. A polaron band narrowing is examined. It is shown that the polymerization of C₆₀ molecules in phase transitions may be caused by the cooperative Jahn-Teller effect. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 8, 521–525 (25 October 1996) Published in English in the original Russian Journal. Edited by Steve Torstveit.     

Yield of singlet oxygen from optically pumped CCl<Subscript>4</Subscript> solution of fullerenes

Boiling occurs in a solution of oxygen and fullerenes in CCl₄ upon optical pumping of C₆₀ upon the fast appearance of incandescent fullerenes in cold solvent. Upon single-photon absorption, a spherical zone of the critical state of CCl₄ is formed within 5 ns (with a diameter of 22–25 nm, P _cr ∼ 45 atm, and T _cr ∼ 556 K). This spherical zone (gas-bubble nucleus) expands to a diameter of ∼100–400 nm for 2–5 ns. If the external pressure (natural or artificial) is rapidly released, the bubble accelerates and emerges into a vacuum chamber within 0.7–25 μs (the length of the passage is 0.1–5 cm depending on the construction of the singlet oxygen generator). We note that singlet oxygen appears 50 ns after the absorption of a photon by fullerene (i.e., inside of the almost formed gas bubble that only begins to emerge from the liquid to a low-pressure gas region).     

Raman scattering of light by optical phonons in Si-Ge-Si structures with quantum dots

Raman scattering of light by optical phonons in Si-Ge-Si structures with pseudomorphic germanium quantum dots has been investigated. Resonance amplification of the scattering intensity on E ₀ (Γ₇−Γ₈) transitions has been observed. It is shown that as a result of the formation of the layer of germanium quantum dots, the resonance energy is ∼0.3 eV higher than in the two-dimensional case. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 3, 203–207 (10 August 1996)     

First observation of optical radiation from fullerenes in the gas phase

Optical radiation of C₆₀ fullerenes in the gas phase was observed. The observed emission line λ=258 nm is identified with an electronic transition into the ground state h _g →h _u in C ₆₀. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 9, 683–687 (10 May 1996)     

Ion-implanted buried layer in diamond as a source of ballistic phonons at liquid-helium temperatures

It is shown that an approximately 150 nm thick ion-implanted buried layer in diamond and excited by a pulsed laser at wavelength λ=337 nm is a source of nonequilibrium acoustic phonons propagating ballistically through the diamond sample at temperatures ∼2 K. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 4, 270–272 (25 August 1996)     

Giant negative magnetoresistance in a nonmagnetic semiconductor

Studies of a classical III–V semiconductor (InSb) doped with 3d magnetic ions (Mn²⁺, having a localized spin S=55/2) reveal some unexpected transport properties. It is found that the transition from the metallic to the low-temperature insulator phase occurs at an impurity concentration N _Mn∼N _cr=2× 10¹⁷ cm⁻³ and a temperature T<T _cr∼1 K. Under these conditions a giant negative magnetoresistance arises. The experimental results can be explained in terms of the onset of a hard Mott-Hubbard gap Δ in the impurity band formed by the shallow manganese acceptor in InSb at N _Mn∼N _cr. A model describing the gap formation is proposed. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 5, 358–362 (10 March 1999) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Low-temperature specific heat of crystalline and amorphous Eu2(MoO4)3

The specific heat C _total of crystalline and amorphous Eu₂(MoO₄)₃ is measured in the temperature interval 4.5–30 K. The amorphous state is obtained by applying pressure ∼7 GPa at room temperature. It is found that the specific heat of the crystal at T⩽7.5 K is described by a cubic function of temperature, while the specific heat of the amorphous sample has a strongly non-Debye character in the entire experimental temperature interval. The curve of C _total for amorphous europium molybdate is analyzed in a model of soft atomic potentials, and it is shown that it agrees well with universal low-temperature anomalies of the specific heat of classical glasses obtained by quenching from the liquid. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 8, 623–627 (25 October 1998)     

Room-temperature Coulomb fingerprints in thin films of a Cu+SiO2 composite material

We study the room-temperature electrical properties of thin (≃200 nm) SiO₂ films with inclusions of Cu globules with radius ≃1 nm and separation ≃20 nm. Current-voltage curves taken across the film in different experimental arrangements show “fingerprints” that are fully reproducible within each setup. We observe multiple peaks with a height of ≃2 pA against the Ohm’s-law background. The typical peak width is consistent with single-electron recharging of Cu globules. We interpret these data as self-selection of energetically favorable quasi-1D chains of globules, along which the current is mainly concentrated. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 10, 684–688 (25 November 1996) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Exchange interactions and spin dynamics in a [CuNd2(C4O4)4(H2O)16]·2H2O crystal

Crystalline [CuNd₂(C₄O₄)₄(H₂O)₁₆]·2H₂O constructed of complexes of trivalent neodymium and divalent copper, has been synthesized and studied by EPR. The square anion groups (C₄O₄) enter as bridge ligands, forming chains of neodymium ions interconnected by (C₄O₄)Cu(C₄O₄) fragments. It is found that the relaxation rate of the neodymium subsystem at room temperature significantly exceeds the exchange interaction rate between copper and neodymium ions. Under these conditions the magnetic properties of the crystal are determined by two magnetically nonequivalent chains of copper ions, which do not interact. The intrachain exchange interaction via hydrogen bonds is estimated to be ∼0.1 cm⁻¹. As one proceeds from the high-temperature (250<T<300 K) to the low-temperature region (T<40 K), a substantial change in the nature of the interaction is revealed. An unusual magnetic structure given in a crystal is observed at low temperatures, which is determined by the presence of two magnetically nonequivalent “ribbons,” formed by the interacting copper and neodymium ions: chains of copper ions are framed on two sides by chains of neodymium ions. The magnitude of the parameter of the exchange interaction between the copper and neodymium ions is estimated as J ^Cu-Nd⩾0.2 cm⁻¹. An exchange interaction between magnetically nonequivalent neodymium ions is not revealed in the EPR spectra. Fiz. Tverd. Tela (St. Petersburg) 39, 2057–2061 (November 1997)     

Colossal magnetoresistance of FexMn1−xS magnetic semiconductors

The magnetic, electric, magnetoresistive, and structural properties are investigated in the sulfide solid solutions Fe_xMn_1−2x S, which are based on the antiferromagnetic semiconductor α-MnS (the fcc NaCl lattice). Colossal negative magnetoresistance (δ_H∼−83% at 160 K for x ∼ 0.29), comparable to that observed in La-Ca-Mn-O polycrystals and films (δ_H∼−90% at 100 K and 40 kOe), is observed in compounds with intermediate concentrations 0.26<x<0.4, corresponding to the region of incipient ferromagnetism. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 12, 895–899 (25 June 1999)     

Pressure-induced polycondensation of C60 fullerene

Modifications of carbon which are formed from C₆₀ fullerite at pressures up to 10.0 GPa and temperatures up to 1900 K are studied by x-ray diffraction, Raman spectroscopy, and atomic force microscopy methods. The pressures p and temperatures T at which atomic, molecular, and polymolecular structures form under conditions of quasihydrostatic compression are determined. It is shown that, together with polymerization, another type of chemical interaction of the molecules, called polycondensation, which leads to the formation of polymolecular structures with a shortest intermolecular distance of 0.65 nm, is possible in the system. Three-dimensional polycondensation of C₆₀ fullerene is explained by the special properties of the new carbon states. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 10, 778–783 (25 May 1996) The spelling of the authors names are presented here in English as requested by the Russian Editorial office.     

Specific features and mechanisms of photoluminescence of nanostructured silicon carbide films grown on silicon in vacuum

The light-emitting properties of cubic silicon carbide films grown by vacuum vapor phase epitaxy on Si(100) and Si(111) substrates under conditions of decreased growth temperatures (T _gr ∼ 900–700°C) have been discussed. Structural investigations have revealed a nanocrystalline structure and, simultaneously, a homogeneity of the phase composition of the grown 3C-SiC films. Photoluminescence spectra of these structures under excitation of the electronic subsystem by a helium-cadmium laser (λ_excit = 325 nm) are characterized by a rather intense luminescence band with the maximum shifted toward the ultraviolet (∼3 eV) region of the spectral range. It has been found that the integral curve of photoluminescence at low temperatures of measurements is split into a set of Lorentzian components. The correlation between these components and the specific features of the crystal structure of the grown silicon carbide layers has been analyzed.     

Subattosecond (⩽10−18 s) time measurements using coherent X-ray transition radiation

The properties of the coherent x-ray transition radiation (CXTR) produced by intense, short electron beams microbunched in various devices, with periods corresponding to x-ray wavelengths ∼0.02–14 nm and with modulation indices ∼0.001–1, are investigated theoretically. The results of numerical calculations show that, just as in the case of incoherent and coherent transition radiation in the optical and microwave regions, CXTR can be used to study the microbunching processes and may thus find application for beam diagnostics in future x-ray FELs and advanced accelerator technology. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 10, 664–668 (25 November 1999) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Structures and energetics of carbon bridged C 60 clusters

The structures and energetics of carbon bridged C₆₀ clusters (C ₆₀ ) _n C_m have been studied by simulated annealing technique within the tight-binding molecular-dynamics. The “sp² addition” ball-and-chain dimers exhibit odd-even alternations over the number of chain atoms, with the dimers containing even chain atoms more stable against dissociation than their immediate neighbors containing odd chain atoms. In addition to the usual “sp² addition” dimers, a pentagon-linked C₁₂₁ isomer and a hexagon-linked C₁₂₂ isomer are also found to be stable. Based on our tight-binding calculations, trimers and larger clusters can be simply regarded as being made up of independent or weakly interacting dimers, if the C-C₆₀ joints on a single cage are not too close to each other. Large C₆₀ clusters connected by chains each containing only one or two carbon atoms have similar stability to that of constituent dimers, indicating the possibility to form stable C₆₀-carbon polymers. Received 17 January 2001 and Received in final form 26 February 2001