CO adsorption on Cu(1 1 1) and Cu(0 0 1) surfaces: Improving site preference in DFT calculations

CO adsorption on Cu(1 1 1) and Cu(0 0 1) surfaces has been studied within ab initio density functional theory (DFT). The structural, vibrational and thermodynamic properties of the adsorbate–substrate complex have been calculated. Calculations within the generalized gradient approximation (GGA) predict adsorption in the threefold hollow on Cu(1 1 1) and in the bridge-site on Cu(0 0 1), instead of on-top as found experimentally. It is demonstrated that the correct site preference is achieved if the underestimation of the HOMO–LUMO gap of CO characteristic for DFT is corrected by applying a molecular DFT + U approach. The DFT + U approach also produces good agreement with the experimentally measured adsorption energies, while introducing only small changes in the calculated geometrical and vibrational properties further improving agreement with experiment which is fair already at the GGA level.     

Magneto-optical spectroscopy of carbon nanotubes

We review our recent optical experiments on single-walled carbon nanotubes in high magnetic fields. The data revealed magnetic-field-induced optical anisotropy as well as broadening, splittings, and shifts of interband absorption and photoluminescence peaks. Quantitative comparison with theoretical predictions based on the Aharonov–Bohm effect is presented.     

CO2-broadened water in the pure rotation and ν2 fundamental regions

The CO₂-broadened water coefficients (half-widths, line shifts, and temperature dependence of the widths) are predicted using a fully complex Robert-Bonamy formulation for the 937 allowed and forbidden perpendicular type transitions of (000)-(000) between 200 and 900 cm⁻¹ in order to facilitate atmospheric remote sensing of Mars and Venus. In addition, empirical Lorentz line widths and pressure-induced frequency-shifts of CO₂-broadened H₂¹⁶O are obtained at room temperature for 257 perpendicular transitions of the (010)-(000) fundamental. For this, calibrated spectra recorded at 0.0054 cm⁻¹ resolution are measured assuming Voigt line shapes. For transitions between 1287 and 1988 cm⁻¹ with rotational quanta up to J = 13 and K_a = 6, the widths vary from 0.045 to 0.212 cm⁻¹ atm⁻¹ at 300 K; the pressure-shifts are quite large and range from −0.0386 to +0.0436 cm⁻¹ atm⁻¹. For the (010)-(000) band, the RMS and mean observed and calculated differences for CO₂-broadened H₂O half-widths are 12% and −1.9%, respectively, while the RMS and mean ratios of the observed and calculated pressure-induced shift coefficients are 1.6 and 0.79, respectively. For pairs of transitions involving K_a = 0 and 1, such as 2_0 2 ← 3_1 3 and 3_1 3 ← 2_0 2, both the calculated and observed pressure induced shifts in positions are opposite in sign and often similar in magnitude. The data are too limited to characterize vibrational dependencies of the widths, however.     

Electrochemical impedance study of lithium-ion insertion into rice husk carbon

Electrochemical impedance spectroscopy (EIS) was employed to study electrochemical behaviors during Li-ion insertion into rice husk carbon. The impedance spectra consist of two depressed semicircles in the high and middle range frequency and an incline line at low frequency. The impedance spectra, obtained in the potential range 2.0 to 0.005 V were analyzed with an equivalent circuit model. Kinetic parameters such as the charge-transfer resistance and surface film resistance were evaluated and discussed. Paper presented at the International Conference on Solid State Science and Technology 2006, Kuala Terengganu, Malaysia, September 4–6, 2006.     

Absolute line intensities of CO2 in the 3090-3920 cm region

Absolute line intensities of ¹³C¹⁶O₂ were retrieved from high-resolution Fourier transform spectra recorded in the region 3090-3920 cm⁻¹. The uncertainty of the line intensity determination is estimated to be between 3 and 5% for the strong lines. The global fittings of the observed line intensities within the framework of the effective operators approach have been performed, reaching the experimental accuracy. A comparison of newly measured line intensities with those found in the HITRAN database is presented.     

Carbon Sphere@Nickel sulfide core-shell nanocomposite for high performance supercapacitor application

The Carbon sphere@Nickel sulfide core-shell nanocomposites for different mole ratios of Carbon sphere (0:1; 0.5:1 and 1:1) have been synthesized by a facile low temperature water-bath method without any further calcination. XRD studies on the core-shell nanocomposites show that characteristic peaks associated with rhombohedral phase structure of nickel sulfide have been retained. TEM morphology presents the interlinked core-shell of Carbon sphere@Nickel sulfide composite with grass-leaf dexterity for better ionic diffusion. BET study confirms the formation of mesoporous structure with high surface area. The existence of elements and its electronic configuration is noted through XPS. The electrochemical studies on pristine nickel sulfide and its Carbon sphere@Nickel sulfide core-shell composites reveal that Carbon sphere@Nickel sulfide (0.5:1) exhibits high specific capacitance of 1022?F?g^?1 at a current density of 1?A?g^?1. It shows good cyclic performance even beyond 4000 consecutive charge/discharge cycles at a relatively high current density of 20?A?g^?1 with the ～83% of retention.     

Fractal and structural aspects of adhesion in particulate-filled polymer composites

Two types of composites based on poly(hydroxy ether) and graphite with various amounts of a filler have been investigated by various methods. The methods have been used to estimate the characteristics of adhesion and interfacial layer, including its thickness and tensile strength and interdependence between these values and adhesion. The results are treated on the basis of the theory of irreversible aggregation, cluster theory of the polymer structure and fractal analysis. It is established that all important characteristics of adhesion, interfacial layer and mechanical properties are interconnected with the difference between fractal dimensions of the surface of the aggregates of filler particles and of a polymer matrix, whose structure is distorted under the influence of the filler surface.     

Flexural reinforcement of concrete floor slabs by carbon fiber textiles

The effect of carbon fiber textile for flexural reinforcement to deteriorated reinforced concrete floor slab is tested in laboratory by cutting out six specimens from existing structure aged more than 70 years. The repair method between concrete and carbon fiber textile is used as experimental parameter. From the test results, deformation, bond characteristic of carbon fiber textile and the applicability of carbon fiber textiles to flexural reinforcement of floor slabs are discussed.     

Evaluation of the performance of high temperature conversion reactors for compound-specific oxygen stable isotope analysis

In this study conversion conditions for oxygen gas chromatography high temperature conversion (HTC) isotope ratio mass spectrometry (IRMS) are characterised using qualitative mass spectrometry (IonTrap). It is shown that physical and chemical properties of a given reactor design impact HTC and thus the ability to accurately measure oxygen isotope ratios. Commercially available and custom-built tube-in-tube reactors were used to elucidate (i) by-product formation (carbon dioxide, water, small organic molecules), (ii) 2nd sources of oxygen (leakage, metal oxides, ceramic material), and (iii) required reactor conditions (conditioning, reduction, stability). The suitability of the available HTC approach for compound-specific isotope analysis of oxygen in volatile organic molecules like methyl tert-butyl ether is assessed. Main problems impeding accurate analysis are non-quantitative HTC and significant carbon dioxide by-product formation. An evaluation strategy combining mass spectrometric analysis of HTC products and IRMS ¹⁸O/¹⁶O monitoring for future method development is proposed.     

Some fractal properties of the percolating backbone in two dimensions

A new algorithm is presented, based on elements of artificial intelligence theory, to determine the fractal properties of the backbone of the incipient infinite cluster. It is found that the fractal dimensionality of the backbone isd _f ^BB =1.61±0.01, the chemical dimensionality isd _t=1.40±0.01, and the fractal dimension of the minimum pathd _min=1.15 ± 0.02 for the two-dimensional triangular lattice.