Manipulation of nanoparticles using dynamic force microscopy: simulation and experiments

82 , M = Sc, Y, La) are discussed. The first ¹³C hyperfine structure has been analyzed in detail and at least seven electronically different groups of carbon atoms could be assigned by simulations of the ESR spectra. The strong similarity of the ¹³C satellite structure suggests the preference of one cage isomer for the scandium group C₈₂ endohedrals. The geometric structure and the electronic structure of all nine fullerene cage isomers of La@C₈₂ were studied by approximate density-functional-based theoretical calculations. A C_3v isomer was found as the most stable one. The manifold of ¹³C hyperfine coupling constants could be interpreted on the basis of the calculated spin density distributions. Received: 15 September 1997/Accepted: 16 October 1997     

Energy and optical absorption spectra of endohedral metallofullerenes with Gd or Ho as strongly correlated π-electron systems

Isomerically pure endohedral metallofullerenes Gd@C82(C2v), Ho@C₈₂(C_2v), and their monoanions have been synthesized and separated. The optical absorption spectra of solutions of obtained compounds in o-dichlorobenzene have been studied. Within the Hubbard model, the energy spectrum of isomer of C_2v symmetry (no. 9) of fullerene С₈₂ has been calculated. Based on the obtained spectrum, optical absorption spectra of endohedral metallofullerenes Gd@C₈₂ and Ho@C₈₂ and their monoanions have been simulated. The calculated optical absorption spectra have been compared with experimental ones; it has been found that qualitative agreement between them is observed.     

Electron affinities of the bromine oxides BrOn,n = 1-4

Bromine oxides are of significant interest due to their importance in atmospheric chemistry. Density functional theory (DFT) methods have been used in conjunction with a DZP++ (double-ζ plus polarization with diffuse functions) basis set to study the molecular geometries and total energies of BrOn and BrO^- _n (n = 1-4). The adiabatic electron affinity (EA_ad), the vertical electron affinity (EA_vert) of the bromine oxide and the vertical detachment energy (VDE) of each anion are reported. Harmonic vibrational frequencies and zero point energies are also reported. Five different DFT methods were employed for comparison. Among these, the BHLYP method predicts the geometries and the vibrational frequencies in best agreement with available experimental data, while the the other methods do better in predicting the limited number of energetic quantities determined observationally. The predicted adiabatic electron affinities are 2.38 eV (BrO, experiment 2.35 eV), 2.36 eV (BrO₂), 3.35 eV (BrOO), 4.32 eV (BrO₃), 2.91 eV (BrOOO) and 5.28 eV (BrO₄). The electronic ground state of BrOO^- is a triplet (³A^") state. Predicted Br–;O bond distances range from 1.61 (BrO₃) to more than 2 Å for Br...O₂ for the neutral molecules; and from 1.61 Å for BrO^- to 1.82 Å for BrO^- to more than 2 Å for Br^-...O₃ among the anions. The BrOO isomer (C_s symmetry) is predicted to lie 17–18 kcal mol^-1 below the C_2v symmetry OBrO structure. The asymmetric ³A^" anion BrOO^- analogously lies below OBrO^-, in this case by 40–41 kcalmol_-1. BrOOO (C_s symmetry) is predicted to lie 42-45 kcalmol-1 below the symmetric C_3v BrO structure. Finally the asymmetric BrOOO- anion (C₁ symmetry) is predicted to lie 10-13kcal mol-1 below symmetric C_3v BrO^- ₃.     

Structures, stabilities, aromaticity, and electronic properties of C66 fullerene isomers, anions (C662?, C664?, C666?), and metallofullerenes (Sc2@C66)

Among all the 4478 classical isomers of C₆₆, C₆₆(C _s :0060) with the lowest number of pentagon–pentagon fusions was predicted to be the most stable isomer, followed by isomers C₆₆(C _2v :0011) and C₆₆(C ₂:0083). The infrared spectra and aromaticity of the most stable isomers were predicted. The relative stabilities of C₆₆ isomers change with charges or doping of metals. The structures and relative stabilities of the most stable metallofullerenes were delineated and compared with experiment. Sc₂@C₆₆(C ₂:0083) was predicted to be the most stable metallofullerene, although Sc₂@C₆₆(C _2v :0011) was observed. Charge-transfer from Sc₂ to the fused pentagons and the bonding between these two moieties significantly decrease the strain energies caused by the pair of fused pentagons thereby stabilizing the fullerene cage.     

Time-resolved Stark effect in rapidly varying fields

The cycle-averaged ac Stark effect associated with the ^[ A _]2Σ⁺v^′=2?^[ X _]2Π1/2v^′=0 two-photon absorption of NO at intensities between 7.7 and 15.2 TW cm^-2 has been characterized in real time through a synergic combination of bichromatic laser experiments and quantum-dynamics calculations. Measurements of the fluorescence emitted by the Rydberg ^[ A _]2Σ⁺v^′=2 level as a function of time between Stark and probe components of a bichromatic field exhibit a characteristic evolution in temporal peak structure with Stark-field intensity, which is interpreted in terms of a time-dependent Floquet analysis of the laser–matter interaction. The experimental observations are consistent with a dynamic Stark shift of Δε_s(ω₁,ω₂)≤0.23 eV of the optical transition at these intensities. Received: 18 January 2002 / Revised version: 6 March 2002 / Published online: 24 April 2002     

Comparison of optical properties and mechanical/electrical degradation of some low density polyethylene-and polypropylene-based polymer blends

In this study, the optical properties as well as mechanical and electrical degradation of low-density polyethylene (LDPE)/polypropylene fiber (PP fiber) (10–50% PP fiber), polypropylene (PP)/PP fiber (10–50% PP fiber), and LDPE/diamond (0.1–3% diamond) blends, which are prepared by hot pressing method, with changing thicknesses ranging from 30 to 225 μm, are compared. The spectra, in the wavelength range 200–2500 nm, are examined. Based on optical absorption spectra obtained, Tauc graphs are plotted. Determined values of the direct optical energy gap (E _d ^opt ), the indirect optical energy gap (E _i ^opt ), the width of the band (ΔE), and ultraviolet transmittance (T_UV) are listed. The direct E _d ^opt and indirect E _i ^opt values for organic blends are in the range of 3.10–3.17 eV and 1.52–2.99 eV; for inorganic blends they are 1.80–4.13 eV and 1.55–4.7 eV respectively. The electrical strength (ε) and the mechanical tension (σ) have been investigated, and graphs (the dependence of the electrical life time log τ_ε on ε) are given. The experimental results are analyzed from the viewpoint of the validity of the thermofluctuation theory. LDPE and LDPE/0.5% diamond composite parameters consecutively changed: σ from 68 to 82 MPa, ε from 60·10⁶ to 85·10⁶ V/m, mechanical lifetime τ_σ from 10 to 1.5·10⁵ sec, electrical lifetime τ_ε from 2· 10³ to 2·10⁵ sec, and structure-sensitive parameters γ and χ — from 1.48 to 1.18 (J)MPa/mole and from 0.97 to 0.70 (J)Vm⁻¹/mole respectively. The values of mechanical and electrical durability were observed to increase by 20 and 41%, respectively, for LDPE/0.5% diamond composite. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 677–683, September–October, 2007.     

Design and First-principles Study of a Fullerene Molecular Device

By using open-ended armchair （6, 6） single-wall carbon nanotubes as electrodes, we investigate the electron transport properties of an all-carbon molecular junction based on the C82 molecule. We find the most stable system among different isomers by performing structural optimization calculations of the Cs2 isomers and the C82 extended molecules. The calculated results show that the C82 -C2 （3） isomer and the C82 extended molecule with C82-C2 isomer are most stable. For the all-carbon hybrid system consisting of C82-C2 extended molecules, it is shown that the Landauer conductance can be tuned over several orders of magnitude both by changing the distance between two electrodes and by changing the orientation of the C82 molecule or rotating one of the tubes around the symmetry axis of the system at a fixed distance. Also, we find the most stable distance between two electrodes from the total energy curve. This fact could make this all-carbon molecular system a possible candidate for a nanoelectronic switch. Moreover, we interpret the conductance mechanism for such a molecular device.     

Ethylene adsorption on the Pt-Cu bimetallic catalysts. Density functional theory cluster study

The adsorption of ethylene on Cu₁₂Pt₂ clusters has been studied within the density functional theory (DFT) approach to understand the high ethylene selectivity of Cu-rich Pt-Cu catalyst particles in the reaction of hydrogen-assisted 1,2-dichloroethane dechlorination. The structural parameters for Cu₁₂Pt₂ clusters with D_4h, D_2d, and C_3v symmetry have been calculated. The relative stability of the isomeric Cu₁₂Pt₂ clusters follows the order: C_3v > D_2d > D_4h. Each isomer has an active site for ethylene adsorption that consists of a single Pt atom surrounded by Cu atoms. The interaction of ethylene with the active site yields a π-C₂H₄ adsorption complex. The strongest π-C₂H₄ complex forms with the cluster of C_3v symmetry; the bonding energy, ΔE_π(C₂H₄), is −15.6 kcal mol⁻¹. The bonding energies for the π-C₂H₄ complex with Cu₁₄ and Pt₁₄ clusters are −6.5 and −18.8 kcal mol⁻¹, respectively.The addition of Pt to Cu modifies the valence spd-band of the cluster as compared to a Cu₁₄ cluster. The DOS near the Fermi level increases when C₂H₄ adsorbs on the Cu₁₂Pt₂ cluster. As well, the center of the d-band shifts toward lower binding energies. Ethylene adsorption also induces a number of states below the d-band. These states correspond to those of gas-phase C₂H₄.The vibrational frequencies of C₂H₄ adsorbed on the clusters of D_4h and C_3v symmetry have been calculated. The phonon vibrations occur below 250 cm⁻¹. The intense bands around 200 cm⁻¹ are attributed to stretching vibrations of the Pt-Cu bonds normal to the cluster surface. The stretching vibrations of the Pt-C bonds depend on the local structure of the active site: ν_s(Pt-C) = 268 cm⁻¹ and ν_as(Pt-C) = 357 cm⁻¹ for the cluster of the D_4h symmetry; ν_s(Pt-C) = 335 cm⁻¹ and ν_as(Pt-C) = 397 cm⁻¹ for the cluster of the C_3v symmetry. Bands in the range of 800-3100 cm⁻¹ are attributed to vibrations of the adsorbed C₂H₄ molecule. The signature frequencies of the π-C₂H₄ adsorption complex are the δ_s(CH₂) deformation vibration at ∼1200 cm⁻¹ and the ν(C-C) stretching vibration at ∼1500 cm⁻¹. These vibration are absent for di-σ-C₂H₄ adsorption complexes.     

The vibrational spectra and structural properties of Me7Eu2UO2(PO4)5 crystals

We investigate the vibrational spectra of crystals of ternary orthophosphates Me₇Eu₂UO₂·(PO₄)₅ (Me–Na, Rb, Cs) obtained by solid-phase synthesis. We show that in these materials the effect of coordination distorts the geometry of the PO ₄ ³⁻ tetrahedron and decreases its symmetry. We conclude that the PO ₄ ³⁻ tetrahedrons in Me₇Eu₂UO₂(PO₄)₅ occupy two nonequivalent positions in the lattice. The character of manifestation and the number of oscillation frequencies observed allow the assumption that they have the C_3v- and C₂-symmetry. This symmetry of two crystallographically nonequivalent groups of PO ₄ ³⁻ ensures a complete set of bands in the IR absorption spectra of the crystals investigated. We show that these crystals exhibit chain structural motifs. Translated from Zhurnal Prikladnoi Spektroskopii, Vol, 64, No. 4, pp. 467–470, July–August, 1997.     

A spectroscopic study of M@C82 metallofullerenes: Raman, far-infrared, and neutron scattering results

82 metallofullerenes have been studied at room temperature by Raman (for M=La, Y, Ce, Gd), far-infrared (FIR) (for M=La, Y, Ce), and inelastic neutron scattering (INS) (for M=La, Y) spectroscopy. Raman and FIR spectra suggest that these metallofullerenes have a common dominant, if not a single, structure of the C₈₂ cage and a similar bonding of the encapsulated metal ion, i.e. the bonding is primarily electrostatic and the metal atoms are in the same oxidation state (+3). The metal ion vibrations are located around 160 and 50 cm^-1. INS reveals no gap between internal vibrational and external vibrational and rotational modes in the range ∼50–200 cm^-1 as is typically observed for other fullerides and also predicted by our model calculations. Presumably this is due to strong intermolecular interactions between M@C₈₂ units in the bulk sample. The studied metallofullerenes are air sensitive, and degradation in air could be followed by changes in the Raman spectra. Received: 24 August 1997/Accepted: 26 September 1997     

Dielectric relaxation,ac and dc conductivities in the fullerenes C60 and C70

The complex conductivity in polycrystalline C₆₀ and C₇₀ has been investigated for frequencies 20 Hz≤ν≤10⁶ Hz and temperatures 10 K≤T≤750 K. The high-frequency dielectric constants ε_α= 2.6±0.1(C₆₀) and ε_∞= 4.6±0.1 (C₇₀) were deduced from these experiments. The observed low temperature relaxation process in C₆₀ fits well into the relaxation dynamics of the C₆₀ molecules as determined by many other experimental techniques operating on very different time scales. In addition to the study of the dipolar relaxation process, the dc and ac conductivities were determined. From the temperature dependence of the dc conductivities energy barriers of E_G=1.75±0.1 eV (C₆₀) and E_G=1.7±0.1 eV (C₇₀) were estimated. In C₇₀ we found indications for small polaron tunneling.     

Driven Tracer Particle in One Dimensional Symmetric Simple Exclusion

Consider an infinite system of particles evolving in a one dimensional lattice according to symmetric random walks with hard core interaction. We investigate the behavior of a tagged particle under the action of an external constant driving force. We prove that the diffusively rescaled position of the test particle εX(ε^-2 t), t > 0, converges in probability, as ε→ 0, to a deterministic function v(t). The function v(⋅) depends on the initial distribution of the random environment through a non-linear parabolic equation. This law of large numbers for the position of the tracer particle is deduced from the hydrodynamical limit of an inhomogeneous one dimensional symmetric zero range process with an asymmetry at the origin. An Einstein relation is satisfied asymptotically when the external force is small. Received: 5 December 1996 / Accepted: 30 June 1997     

Production, isolation, and characterization of group-2 metal-containing endohedral metallofullerenes

80 , Ca/Sr/Ba@C₈₂, Ca/Sr/Ba@C₈₄) are investigated for the first time by UV-Vis-NIR absorption spectroscopy and high-resolution ¹³C NMR. Direct evidence of the endohedral nature and cage structures are revealed by these measurements. Furthermore, we have found that each metallofullerene has 2–4 structural isomers, which have been isolated by multistage high-performance liquid chromatography. These isomers have different cage structures and give characteristic UV-Vis-NIR absorption spectra. Received: 22 September 1997/Accepted: 16 October 1997     

The dielectric function of potassium-doped zinc-phthalocyanine

We have studied the electronic excitations of potassium-doped zinc-phthalocyanine using electron energy-loss spectroscopy. This allowed the determination of the complex dielectric function ε(ω) in an energy range between 0 and 70 eV. Our results reveal distinct changes of the electronic excitation spectra going from ZnPc to K₄ZnPc. They can be used as data basis for future optical characterization of potassium-doped ZnPc films. PACS 71.20.Rv; 78.20.-e     

Experimental and theoretical study of the IR absorption spectrum of 2,4-oxazolidinedione

The IR absorption spectra of 2,4-oxazolidinedione in tablet and solution form were measured over the frequency range 400–3600 cm^–1. The complete set of normal modes for the molecule are calculated on the basis of a mechanical model with symmetry C_s. The spectrum is interpreted. The spectral features can be explained by taking into account the strict C_s symmetry of the molecule as a whole and the approximate C_2v symmetry with traces of D_5h for the ring.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 27–32, September, 1970.     

Nonlinear optical spectroscopy of electronic transitions in hexagonal manganites

The hexagonal rare-earth manganites RMnO₃ (R = Sc, Y, Ho, Er, Tm, Yb, Lu) are a group of materials with an unusual combination of magnetic, electric and optical properties. The electronic structure of these materials was studied by second harmonic (SH) spectroscopy in the range from 1.2 to 3.0 eV. Faraday rotation and absorption spectra were measured in the range from 1.0 to 1.6 eV. Broad bands at ∼1.7 eV and ∼2.7 eV are assigned to electronic transitions between Mn³⁺(3d⁴) levels. The SH spectra are discussed on the basis of a recently developed microscopic theory. Received: 26 April 2001 / Published online: 18 July 2001     

Search for solar axions generated by the Primakoff effect with resonance absorption by <Superscript>169</Superscript>Tm

We searched for resonant excitation of the first excited state of the ¹⁶⁹Tm nucleus by axions formed inside the Sun by the Primakoff effect, A + ¹⁶⁹Tm → ¹⁶⁹Tm* → ¹⁶⁹Tm + γ (8.41keV). Gamma quanta with an energy of 8.41keV were registered by a sectionalized Si(Li) detector installed in a low-background setup. As a result, we set a new upper limit for the photon to axion coupling constant, g _Aγ (GeV⁻¹)m _A (eV) ≤ 1.06 × 10⁻⁵, which for a hadronic axion model corresponds to a mass limit of m _A ≤ 169 eV at a 90% confidence level.     

Vibrational Spectra and Normal Coordinate Analysis of Diamminediiodidezinc(II) with 15N and 2H Isotopic Substitution.

The Raman and IR. spectra of solid diamminediiodidezinc (II) with ¹⁵N and ²H isotopic substitution have been measured. The spectra have been interpreted assuming C_2v symmetry for the Zn(NH₃)₂I₂ complex structure. The skeletal stretching metal-ligand modes v_s(ZnN), v_as(ZnN), v_s(ZnI), v_as(ZnI) as well as the three bending modes δ(NZnN), δ(IZnI) and δ(IZnN) were assigned by comparison with the spectra of Zn(NH₃)₂C1₂ and Zn(NH₃)₂Br₂, and by the observed isotopic shifts of the frequencies. A normal coordinate analysis for the whole complex was carried out using the Local Symmetry Force Field Model.     

Studies of third-order nonlinear optical properties of C60 by the optical Kerr effect

60 at 1.064 μm is determined by the optical Kerr effect in toluene solution. Values of -6.5×10^-33 esu and 2.0×10^-32 esu for the real and imaginary parts of γ, respectively, are obtained. Based on the experimental results and symmetry constraint, it is concluded that a three-level model is not adequate to describe the third-order nonlinearity of C₆₀. It is also inferred that the non-resonant γ of C₆₀ should be positive in sign, which is in agreement with reported off-resonant measurements of γ of C₆₀ by third-harmonic generation. Received: 3 September 1997/Revised version: 1 December 1997     

Effects of spatial dispersion at intraband transitions in multiple quantum well structures

Effects of spatial dispersion in reflection of light from multiple quantum well structures of different symmetry have been investigated. It has been shown that with inclined incidence of linearly polarized light on the system of symmetry C _∞v , the reflected wave starts to manifest the circular polarization. Upon the incidence of s(p)-polarized light on the structure of the D _2d symmetry, the reflected wave starts to manifest p(s) component, while in the case of the point symmetry C _2v , this phenomenon also occurs for the normal incidence. The magneto-spatial dispersion in the magnetic field lying in the structure plane leads to the same conversion of polarization. Dependences of the polarization-sensitive reflection coefficients on the incidence angle are calculated. The microscopically gyrotropic contributions to the dielectric permittivity of the multiple quantum well structures are calculated for the intraband frequency range. Evaluations show that the effects of spatial dispersion in such systems can be observed experimentally.