Self-assembly of C60 fullerenes on quasi-one-dimensional Si(111)4 × 1-In surface

Using scanning tunneling microscopy observations, self-assembly of C₆₀ fullerenes in the course of room-temperature adsorption onto Si(111)4 × 1-In reconstruction and after subsequent annealing at temperatures ranging from 150 to 450 °C has been studied. Adsorbed C₆₀ fullerenes have been found to occupy off-centered positions on In-atom rows forming linear chains with a maximal length of eight C₆₀ molecules. Intermolecular spacing within the regular chains equals three lattice constants of Si(111) surface. Two energetically different adsorption states of C₆₀ have been detected, one of which is occupied preferentially at room temperature, while occupation of the second (more tight) state dominates at temperature above ~ 150 °C. In the first state, C₆₀ fullerene resides plausibly in a continuous rotation, while in the second state a C₆₀ molecule is fixed tightly in a single orientation with a C₆₀ hexagon pointing upward. Transition of C₆₀ fullerenes to the more stable state is accompanied by expelling In atoms from the Si(111)4 × 1-In reconstruction.     

UV–Vis and NMR spectroscopic investigations on effective and selective non-covalent interactions between fullerenes and calix[6]arene

Ground state non-covalent interactions between a macro cyclic calixarene receptor, namely, 4-tert-butylcalix[6]arene (1), and fullerenes (C₆₀ and C₇₀) were studied in toluene medium by absorption spectrophotometric method. Absorption band due to the charge transfer (CT) transition have been observed in the visible region between fullerenes and 1. Utilizing the CT absorption bands, various important physicochemical parameters like oscillator strength, resonance energy, transition dipole strength of the fullerene-1 complexes and ionization potential of 1 is determined in present investigations. From Jobs method of continuous variation, it is observed that both C₆₀ and C₇₀ form stable 1:1 complexes with 1. The most fascinating feature of the present study is that 1 binds selectively C₇₀ compared to C₆₀ as obtained from binding constant (K) data of C₆₀–1 (K_C60–1) and C₇₀–1 (K_C70–1) complexes, i.e., K_C60–1 = 32,400 dm³·mol^? 1 and K_C70–1 = 110,000 dm³.mol^? 1 and selectivity (K_C70–1/K_C60–1) = 3.4. ¹H NMR analysis provides very good support in favor of strong binding between C₇₀ and 1.     

Thin films of molecule-based charge transfer complex cobalt tetracyanoethylene: In situ X-ray photoemission study

Thin films of molecule-based charge transfer magnet, cobalt tetracyanoethylene [Co(TCNE)_x, x ~ 2] consisting of the transition metal Co, and an organic molecule viz. tetracyanoethylene (TCNE) have been deposited by using physical vapor deposition method under ultra-high vacuum conditions at room temperature. X-ray photoelectron spectroscopy (XPS) technique has been used extensively to investigate the electronic properties of the Co(TCNE)_x thin films. The XPS measurements show that the prepared Co(TCNE)_x films are clean, and oxygen free. The stoichiometries of the films, based on atomic sensitive factors, are obtained, and yields a ~ 1:2 ratio between metal Co and TCNE for all films. Interestingly, the positive shift of binding energy position for Co(2p), and negative shifts for C(1s) and N(1s) peaks suggest a charge-transfer from Co to TCNE, and cobalt is assigned to its Co(II) valence state. In the valence band investigation, the highest occupied molecular orbital (HOMO) of Co(TCNE)_x is found to be at ~ 2.4 eV with respect to the Fermi level, and it is derived either from the TCNE^? singly occupied molecular orbital (SOMO) or Co(3d) states. The peaks located at ~ 6.8 eV and ~ 8.8 eV are due to TCNE derived electronic states. The obtained core level and valence band results of Co(TCNE)_x, films are compared with those of V(TCNE)_x thin film magnet: a well known system of M(TCNE)_x type of organic magnet, and important points regarding their electronic properties have been brought out.     

Interaction between fullerene-wheeled nanocar and gold substrate: A DFT study

Since the successful synthesis of nanocar and its surprising movement on the gold surface, several theoretical investigations have been devoted to explain the interaction properties as well as its movement mechanism on the substrate. All of them failed, however, to gain a clear theoretical insight into the respected challenges because of the weak computational methods implemented for this complex system including heavy metal atoms and giant size of the whole system. In this work, we have investigated the adsorption of fullerene-wheeled nanocar onto a Au (1 1 1) substrate using the comprehensive first-principles density functional theory (DFT) simulations. The binding energy between the nanocar and Au (1 1 1) surface was determined to be −9.43 eV (−217.45 kcal/mol). The net charge transfer from the nanocar to the gold substrate was calculated to be about 9.56 electrons. Furthermore, the equilibrium distances between the Au surface and the C₆₀ molecule and nanocar chassis were estimated to be 2.20 Å and 2.30 Å, respectively. The BSSE correction was also considered in the binding energy estimation and the result show that the BSSE correction significantly affects the calculated binding energy for such systems.Finally, we have performed ab initio molecular dynamics simulation for a single C₆₀ fullerene on the gold surface at room temperature. Our first-principles result shows that ambient condition affect remarkably on the adsorption property of fullerene on the gold surface. We also observed that the C₆₀ fullerene wheel slips by approximately 3.90 Å within 5 ps of simulation time at 300 K.     

Ultrafast photoisomerization and its single-shot pump pulse efficiency of trans-azobenzene derivative: Compound for photosensitive DNA

The femtosecond photoisomerization processes of trans (T) 4-carboxy-2′,6′-dimethylazobenzen, which has been employed recently as an efficient photoregulator of DNA hybridization, were clarified by the rate equation analysis of measured transient absorbance changes with (350 nm) and without (380 nm) ground-state absorption of both the reactant (T) and photoproduct (cis: C) isomers under S₂^T-band excitation (360 nm, 150 fs pump): after excitation to the S₂^T state with a 450-fs lifetime, ~ 1.5% of the T-molecules in the S₂^T state are isomerized to the C-form within ~ 6 ps through the intermediate state (so called bottleneck state), but most of those return back to the T ground-state S₂^T via the internal conversion processes with an ultrafast kinetic rate of 2.2 × 10¹² s^? 1. Moreover, the rate equation analysis enables us to determine the T-to-C photoisomerization rate η^T,C per pump pulse to be 0.0011 at the pump energy of 80 nJ from the amplitude A_3,350 of the offset component in the 350-nm probe signal, and to obtain the photoisomerization quantum yield Φ^T,C = 0.094. The latter value is slightly lower than that of T-azobenzene, and well agrees with that (Φ^T,C = 0.097) measured by the conventional CW irradiation method using a photostationary state.     

Adsorption of thiophene on silica-supported Mo clusters

The adsorption/decomposition kinetics/dynamics of thiophene has been studied on silica-supported Mo and MoS_x clusters. Two-dimensional cluster formation at small Mo exposures and three-dimensional cluster growth at larger exposures would be consistent with the Auger electron spectroscopy (AES) data. Thermal desorption spectroscopy (TDS) indicates two reaction pathways. H₄C₄S desorbs molecularly at 190–400 K. Two TDS features were evident and could be assigned to molecularly on Mo sites, and S sites adsorbed thiophene. Assuming a standard preexponential factor (ν = 1 × 10¹³/s) for first-order kinetics, the binding energies for adsorption on Mo (sulfur) sites amount to 90 (65) kJ/mol for 0.4 ML Mo exposure and 76 (63) kJ/mol for 2 ML Mo. Thus, smaller clusters are more reactive than larger clusters for molecular adsorption of H₄C₄S. The second reaction pathway, the decomposition of thiophene, starts at 250 K. Utilizing multimass TDS, H₂, H₂S, and mostly alkynes are detected in the gas phase as decomposition products. H₄C₄S bond activation results in partially sulfided Mo clusters as well as S and C residuals on the surface. S and C poison the catalyst. As a result, with an increasing number of H₄C₄S adsorption/desorption cycles, the uptake of molecular thiophene decreases as well as the H₂ and H₂S production ceases. Thus, silica-supported sulfided Mo clusters are less reactive than metallic clusters. The poisoned catalyst can be partially reactivated by annealing in O₂. However, Mo oxides also appear to form, which passivate the catalyst further. On the other hand, while annealing a used catalyst in H/H₂, it is poisoned even more (i.e., the S AES signal increases). By means of adsorption transients, the initial adsorption probability, S₀, of C₄H₄S has been determined. At thermal impact energies (E_i = 0.04 eV), S₀ for molecular adsorption amounts to 0.43 ± 0.03 for a surface temperature of 200 K. S₀ increases with Mo cluster size, obeying the capture zone model. The temperature dependence of S₀(T_s) consists of two regions consistent with molecular adsorption of thiophene at low temperatures and its decomposition above 250 K. Fitting S₀(T_s) curves allows one to determine the bond activation energy for the first elementary decomposition step of C₄H₄S, which amounts to (79 ± 2) kJ/mol and (52 ± 4) kJ/mol for small and large Mo clusters, respectively. Thus, larger clusters are more active for decomposing C₄H₄S than are smaller clusters.     

Carbon doping of MgB2 by toluene and malic-acid-in-toluene

The decomposition of malic acid (C₄H₆O₅) in the presence of Mg and B was studied using Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA) which revealed that malic acid reacted with Mg but not B. Also, the addition of toluene (C₇H₈) to dissolve malic acid followed by subsequent drying resulted in no reaction with Mg, indicating that the malic acid had decomposed during the dissolution/drying stage. The total carbon contributed by toluene versus a toluene/5 wt.% malic acid mixture was measured using a LECO CS600 carbon analyzer. The toluene sample contained ～0.4 wt.% C while the toluene/malic acid mixture had ～1.5 wt.% C, demonstrating that the toluene contributed a significant amount of carbon to the final product. Resistivity measurements on powder-in-tube MgB₂ monofilamentary wires established that the toluene/malic acid doped sample had the highest B_c2. However, the toluene-only sample had the highest transport J_c over most of the magnetic field range (0–9 T), equaled only by that of toluene/malic-acid sample in fields above 9 T.     

Monitoring of laser heating temperature in laser spectroscopic measurements

During laser spectroscopic measurement, a part of laser energy will be converted into heat in the processes of excitation and light emission. Temperature monitoring can help to evaluate such nonradiative process. Upconversion luminescence of phosphor Y₂O₃:Er,Yb under laser excitation at 980 nm was investigated in this work. Point temperature of the phosphor was monitored using the fluorescent intensity ratio (FIR) technology. Laser induced temperature rising was identified by comparison with a theoretically ideal temperature calibration function: lnR = 3.1738–1167/T. The monitored temperature of laser heating rises monotonically with increasing laser power. Circumstances around heating point will modify the calibration function, but the linear slope of lnR ~ 1/T is constant.     

Spontaneous formation of size-selected bimetallic nanoparticle arrays

An original physical route is proposed to organize size-selected bimetallic nanoparticles on graphite surfaces. This approach is based on the soft landing of preformed clusters and is demonstrated for bimetallic Au_xPt_1 ? x clusters of different compositions. Particle coalescence is avoided thanks to cluster surface reactivity, leading to a self-assembly with a well-defined inter-particle separation (~ 1 nm).     

Terahertz emission dependence on the intensity ratio of 400–800 nm in generating terahertz waves from two-color laser-induced gas plasma

A transient photocurrent model is used to explain terahertz emission from gas plasma irradiated by a laser pulse and the second harmonic. By introducing the second harmonic, 400 nm, the corresponding terahertz emission is greatly enhanced. The exact dependence of terahertz emission on the intensity ratio of 400–800 nm is studied for the case with total intensity of 5.00 × 10¹⁴ W/cm². Results show the emission reaches the maximum at about the case for energy distribution of I_ω = 4.00 × 10¹⁴ W/cm², I_2ω = 1.00 × 10¹⁴ W/cm².     

The growth and field evaporation of Er and deuterated Er films

The morphological structure of clean and deuterated Er films deposited on W substrates and their removal by field evaporation have been investigated as part of a program directed toward the development of deuterium ion sources for neutron generators. Annealed Er films up to ~ 20 monolayers in thickness deposited on W < 110 > substrates appear pseudomorphic. Thicker annealed films form a hexagonal close-packed < 0001 > orientated over-layer with the Pitsch–Schrader orientation relation. The pseudomorphic and hexagonal close-packed character of the films is retained up to the last atomic layer that forms the film-substrate interface. Deuterated Er films appear polycrystalline. At 77 K in Ar, annealed Er films field evaporate at 2.5 V/Å primarily as Er^2 + and deuterated Er films evaporate at ~ 2.4 V/Å primarily as ErD_x^2 +. Field evaporation of both clean and deuterated Er films shows signs of space charge induced field lowering when film thicknesses exceeding ~ 10 layers were field evaporated using 20 ns duration voltage pulses.     

Kinetics for the reactions of phenyl with methanol and ethanol: Comparison of theory and experiment

The kinetics of the C₆H₅ reactions with CH₃OH and C₂H₅OH has been measured by pulsed-laser photolysis/mass-spectrometry (PLP/MS) employing acetophenone as the radical source. Kinetic modeling of the benzene formed in the reactions over the temperature range 306–771 K allows us to reliably determine the total rate constants for H-abstraction reactions. In order to improve our low temperature measurements down to 304 K we have also applied the cavity ring-down spectrometric technique using nitrosobenzene as the radical source. Both sets of data agree closely. A weighted least-squares analysis of the two complementary sets of data for the two reactions gave the total rate constants k(CH₃OH) = (7.82 ± 0.44) × 10¹¹ exp [?(853 ± 30)/T] and k(C₂H₅OH) = (5.73 ± 0.58) × 10¹¹ exp [?(1103 ± 44)/T] cm³ mol^?1 s^?1 for the temperature range studied. Theoretically, four possible product channels of the C₆H₅ + CH₃OH reaction producing C₆H₆ + CH₃O, C₆H₆ + CH₂OH, C₆H₅OH + CH₃ and C₆H₅OCH₃ + H and five possible product channels of the C₆H₅ + C₂H₅OH reaction producing C₆H₆ + C₂H₅O, C₆H₆ + CH₂CH₂OH, C₆H₆ + CH₃CHOH, C₆H₅OH + CH₃CH₂ and C₆H₅OCH₂CH₃ + H have been computed at the G2M//B3LYP/6?311+G(d, p) level of theory. The hydrogen abstraction channels were predicted to have lower energy barriers than those for the substitution reactions and their rate constants were calculated by the microcanonical variational transition state theory at 200–3000 K. The predicted rate constants are in good agreement with the experimental values. Significantly, the rate constant for the CH₃OH reaction with C₆H₅ was found to be greater than that for the C₂H₅OH reaction and both reactions were found computationally to be dominated by H-abstraction from the hydroxyl group attributable to the affinity of the phenyl toward the OH group and the predicted lower energy barriers for the OH attack.     

Fluorine etching on the Si(111)-7×7 surfaces using fluorinated fullerene

Fluorine etching on the Si(1 1 1)-7×7 surfaces using fluorinated fullerene molecules as a fluorine source has been investigated. At room temperature, adsorbed fluorinated fullerene molecules reacted with the Si(1 1 1)-7×7 surface to create a localized distribution of fluorine on the surface. Nanoscale etch pits were created by annealing at 300 °C, due to the adsorption of the fluorine localized around the C₆₀F_x molecules. Annealing at 400 °C resulted in the delocalized fluorine distribution on the surface and healing of the etch pits, due to the enhancement of the diffusion of both the fluorine and silicon atoms. Subsequent annealing at 500 °C led to desorption of SiF₂ reactants formed on the surface. The fluorine diffusion process was found to be an elemental process in the etching because the diffusion of adsorbed fluorines is a key for the formation of the SiF₂ species and their subsequent desorption.     

Critical temperature and orthorhombicity of Y2Ba4Cu7O15−δ

Superconducting properties have been systematically studied for oxygen content controlled Y₂Ba₄O₇O_15?δ (Y247) polycrystalline bulks sintered under various conditions, 940–975 °C and P(O₂) = 4–16 atm. T_c of oxygen annealed Y247 samples at 400 °C varied largely depending on the sintering conditions from ～60 to ～90 K. Samples sintered under higher P(O₂) exhibited lower T_c, whereas they were confirmed to be of Y247 single phase by powder X-ray analyses. Strong relationship between orthorhombicity defined as 1000(b ? a)/(a + b) and T_c was found in Y247 as in the cases of REBa₂Cu₃O_7?δ with light rare-earth elements, such as La, Nd, Sm, Eu and Gd. In addition, T_c‘s of samples with nominal compositions of Y_2+xBa_4?xO₇O_15?δ systematically decreased with an increase of x. These results indicated that partial substitution of Y for Ba occurred in the Y247 compounds possibly due to high occupancy ratio of oxygen at the Cu–O_1-δ chain during the sintering process.     

Improvement of stability and pulse energy in a diode-pumped dual-loss-modulated QML Nd:Lu0.2Y0.8VO4 laser with EO modulator and GaAs

The Q-switched and mode-locked (QML) performance in a diode-pumped Nd:Lu_0.2Y_0.8VO₄ laser with electro-optic (EO) modulator and GaAs saturaber absorber is investigated. In comparison with the solely passively QML laser with GaAs, the dual-loss-modulated QML laser with EO and GaAs can generate pulses with higher stability and shorter pulse width of Q-switched envelope, as well as higher pulse energy. At the repetition rate 1 kHz of EO, the pulse width of Q-switched pulse envelope has a compression of 89% and the pulse energy has an improvement of 24 times. The QML laser characteristics such as the pulse width, pulse peak power etc. have been measured for different small-signal transmittance (T₀) of GaAs, different reflectivity (R) of output coupler and modulation frequencies of the EO modulator (f_e). The highest peak power and the shortest pulse width of mode-locked pulses are obtained at f_e = 1 kHz, R = 90% and T₀ = 92.6%. By considering the influences of EO modulator, a developed rate equation model for the dual-loss-modulated QML laser with EO modulator and GaAs is proposed. The numerical solutions of the equations are in good agreement with the experimental results.     

HREELS study of C70 molecules adsorbed on a Si(1 1 1)-(7×7) surface

We have measured the coverage dependence of vibrational excitation spectra of C₇₀ molecules adsorbed on a Si(1 1 1)-(7×7) surface using high-resolution electron-energy-loss spectroscopy. At the monolayer coverage, the intensity of the 57 meV peak increases, and those of the 83 and 178 meV peaks decrease. Taking into account the dipole selection rule, the change in intensity of the 57 meV peak indicates that the average angle between the long axes of C₇₀ molecules and surface normal is about 40°. The decreases in intensities of the 83 and 178 meV peaks suggest that the rotational motion of molecules is quenched upon adsorption. We will discuss the Coriolis interaction between the accidentally degenerate A₂″ and E₁′ modes.     

The influence of thermal lens effect on pulse repetition rate in diode-pumped passively Q-switched Nd:GdVO4/V:YAG laser

The influence of thermal lens effect on pulse repetition rate in diode-pumped Nd:GdVO₄ 1.34 μm laser has been demonstrated. The repetition rate first increased, then reduced with augment of the pump power, for V:YAG with initial transmission (T₀) of 96%. The maximum repetition rate was 70 kHz, obtained at the pump power of 6.78 W. The best output laser characteristics—the pulse width of 39.2 ns, the peak power of 2.5 kW and the single pulse energy of 102 μJ—were obtained by V:YAG of T₀=89%. With the Gaussian spatial distribution of intracavity photon density being considered, the rate equations were solved numerically and the theoretical calculations agreed with the experimental results.     

Recombination luminescence of CsI(Tl) under electron pulse irradiation

The luminescence kinetics of CsI(Tl) exposed to an electron pulse irradiation (E_e = 250 keV, t_1/2 = 10 ns, j = 2 ÷ 160 mJ/cm²) has been studied. It has been discovered that the slow emission rise is due to hole V_k–Tl⁰ recombination luminescence at temperature from 100 to 160 K and electron–V_kA recombination, where electrons released from single Tl⁰ at temperature from 180 to 300 K. The effect of Tl concentration on both processes has been investigated.     

Transitional metal-doped 8 mol% yttria-stabilized zirconia electrolytes

The sintering, grain growth and ionic conductivities (especially the grain-boundary (GB) conductivity), of 8YSZ electrolytes with various silica levels (~ 30 ppm, ~ 500 ppm and ~ 3000 ppm), doped with 1 at% transitional metal oxides (TMOs), have been systematically investigated by means of dilatometer, electron microscopy and impedance analyzer. It is confirmed that small additions of TMOs (i.e., Fe, Mn, Co or Ni) promote the densification and grain growth of both the pure and Si-containing 8YSZ. The effect of TMOs on the ionic conductivities could be negative or positive, relying on the type of TMOs, sintered density and impurity level. For the dense and pure 8YSZ (with ~ 30 ppm SiO₂), the addition of 1 at% TMOs led to a reduction in grain interior (GI) conductivity by ~ 25–33% with little effect on the GB conduction. For the impure 8YSZ (with ~ 500 ppm or 3000 ppm SiO₂), except for FeO_1.5, the other TMOs (i.e., Mn, Co or Ni) are extremely detrimental to the total conductivity by significantly reducing the GB conduction. Moreover, it is also found that the GB conductivity of the impure 8YSZ doped with Co or Ni is less sensitive to sintering temperature. FeO_1.5 showed a scavenging effect on SiO₂ in the impure 8YSZ, which is specially beneficial to the total conductivity of samples with higher silica levels and/or sintered at relatively low temperatures.