Profile imaging of reconstructed polar and non-polar surfaces of ZnO

The atomic scale surface structures of ZnO non-polar as well as and ±(0 0 0 1) polar surfaces have been directly imaged by high-resolution transmission electron microscopy (HRTEM). The observations were made on clean surfaces created by irradiating a single ZnO nanobelt using 400 keV electron beam in TEM, under which ZnO dots were grown epitaxially and in situ on the surface of the nanobelt. A technique is demonstrated for directly distinguishing the surface polarity of the ±(0 0 0 1) polar surfaces. For the non-polar surface, HRTEM images and simulation results indicate that the Zn ions in the first and second layer suffer from inward and outward relaxation, respectively; the oxygen ions in the first and second layer prefer shifting to vicinal Zn ions to shorten the bonding distance. For the oxygen-terminated polar surface, the oxygen ions at the outmost top layer were directly imaged. a × 2 reconstruction has also been observed at the surface, and its atomic structure has been proposed based on image simulation. Oxygen-terminated polar surface is flat and shows no detectable reconstruction. For the Zn-terminated (0 0 0 1) polar surface, HRTEM may indicate the existence of Zn vacancies and a possibly c-axis, random outward displacement of the top Zn ions. Our data tend to support the mechanism of removal of surface atoms for maintaining the stability of (0 0 0 1) polar surfaces.     

L to M shell transitions and model comparisons for radiative opacities of sodium fluoride plasma

The radiative opacities of hot dense sodium fluoride (NaF) plasma have been studied in the case of local thermodynamic equilibrium (LTE). The spectrally resolved opacity in the case of and is taken as an example to illustrate the absorption structures of the NaF plasma. The transitions from L to M shells of sodium and fluoride are the main contributions for the plasma absorptions. The isodense opacities of NaF plasma are studied at a density of and temperatures of 20-60 eV. Detailed comparisons among the results of the detailed term accounting (DTA), detailed configuraion accounting (DCA), unresolved transition array (UTA) and average atom (AA) model codes, which have been developed independently in China in the past few years, are performed for both the spectral resolved and mean opacities. Good agreements are found at a temperature of 40 eV and a density of , but discrepancies appear at a temperature of 50 eV and a density of .     

Surface-energy-anisotropy-induced orientation effects on Rayleigh instabilities in sapphire

Arrays of controlled-geometry, semi-infinite pore channels of systematically varied crystallographic orientation were introduced into undoped m-plane sapphire substrates using microfabrication techniques and ion-beam etching and subsequently internalized by solid-state diffusion bonding. A series of anneals at 1700 °C caused the breakup of these channels into discrete pores via Rayleigh instabilities. In all cases, channels broke up with a characteristic wavelength larger than that expected for a material with isotropic surface energy, reflecting stabilization effects due to surface-energy anisotropy. The breakup wavelength and the time required for complete breakup varied significantly with channel orientation. For most orientations, the instability wavelength for channels of radius R was in the range of 13.2R-25R, and complete breakup occurred within 2-10 h. To first order, the anneal times for complete breakup scale with the square of the breakup wavelength. Channels oriented along a direction had a wavelength of ≈139R, and required 468 h for complete breakup. Cross-sectional analysis of channels oriented along a direction showed the channel to be completely bounded by stable c(0 0 0 1), , and facets.     

MRCI studies on the electronic structure of AlN and AlN, and the electron affinity of AlN

Using multireference configuration-interaction methods and double to triple-zeta basis sets with semidiffuse and polarization functions, potential energies and spectroscopic constants for low-lying doublet, and quartet states of AlN⁻ were calculated. has R_e=3.280 bohr and . lies 0.17 eV above the ground state. Using an estimated electron affinity of 2.1 eV for AlN, four states of AlN⁻ are found to be stable, namely , , , and . Comparisons with the isovalent anions BN⁻ (three stable states) and AlP⁻ (seven stable states) are made. Photo-detachment of an electron from the state of AlN⁻ can lead to an accurate determination of the energy difference between the two close-lying lowest states of AlN, and , predicted here to be 0.09 eV apart.     

Modelling of phase transitions and reaction at CO adsorption on oxygen precovered Pd(1 1 1)

Using the interaction parameters up to the third neighbors and activated form of O and CO diffusion and their reaction, the model has been proposed for Monte-Carlo simulations describing the catalytic O + CO → CO₂ reaction and occurring phase transitions on Pd(1 1 1) surface. Upon adsorption of CO the pre-adsorbed oxygen transforms from p(2 × 2)_O phase into and phases in the limit of room and moderate temperatures, respectively. We demonstrate that the kinetic effects determine both the occurrence of the p(2 × 1)_O and disappearance of the phases at moderate and low temperatures, respectively. Using reaction rate as a fit parameter, we show that at room temperature the start of the reaction can be synchronized with the occurrence of phase.     

Time-resolved spectroscopy of Al, Ti, and Mo X pinch radiation using an X-ray streak camera

Time-resolved spectroscopic measurements of the radiation emitted from Al, Ti, and Mo X pinches have been made with time resolution. The radiation is emitted from micropinch plasmas with sizes of order in times in the 10- range. Spectra implied that dense, plasmas were produced, such as a lifetime, 1.5- electron temperature and near solid-density Ti plasma. The experimental systems and analysis methods are described in detail, including line ratio calculations for μm-scale Ti and Al plasmas with ion densities of 10¹⁹-10²⁴ cm⁻³ and electron temperatures.     

The v6 = 1 and v6 = 2 vibrational states of DCF3

The high-resolution infrared spectra of DCF₃ were reinvestigated in the ν₆ fundamental band region near 500 cm⁻¹ and around 1000 cm⁻¹ with the aim to assign and analyze the overtone level of the asymmetric CF₃ bending vibration v₆ = 2.The present paper reports on the first study of both its sublevels (A₁ and E corresponding to l = 0 and ±2, respectively) through the high-resolution analysis of the overtone band and the hot and bands.The well-known “loop method”, applied to and , yielded ground state energy differences Δ(K, J) = E₀(K, J) − E₀(K − 3,J) for the range of K = 6 to 30.In the final fitting of molecular parameters, we used the strategy of fitting all upper state data together with the ground state rotational transitions.This is equivalent to that calculating separately the and coefficients of the K-dependent part of the ground state energy terms from the combination loops.All rotational constants of the ground state up to sextic order could be refined in the calculation.This led to a very accurate determination of C₀ = 0.18924413(25) cm⁻¹, , and also .In the course of analyzing simultaneously the overtone band together with the and ν₆ bands, the original assignment of the fundamental ν₆ band [Bürger et al., J. Mol. Spectrosc. 182 (1997) 34-49] was found to be incompatible with the present one. Assignments of the (k + 1, l₆ = +1)/(k − 1,l₆ = −1) levels had to be interchanged, which changed the value of Cζ₆ = −0.14198768(26) cm⁻¹ and the sign of the combination of constants C − B − Cζ in the v₆ = 1 level to a negative value.     

Aromatic interactions in the close packing of phenyl-imides at Cu(1 1 0) surfaces

The oxidation of aniline at Cu(1 1 0) surfaces at 290 K has been studied by XPS and STM. A single chemisorbed product, assigned to a phenyl imide (C₆H₅N(a)), is formed together with water which desorbs. Reaction with preadsorbed oxygen results in a maximum surface concentration of phenyl imide of 2.8 × 10¹⁴ mol cm⁻² and a surface dominated by domains of three structures described by , and unit meshes. However, concentrations of phenyl imide of up to 3.3 × 10¹⁴ mol cm⁻² were obtained from the coadsorption of aniline and dioxygen (300:1 mixture) resulting in a highly ordered biphasic structure with and domains. Comparison of the STM and XPS data shows that only half the phenyl imides at the surface are imaged. Pi-stacking of the phenyl rings is proposed to account for this observation.     

A novel approach to measure the step line tension and the step dipole moment on vicinal Au(0 0 1) electrodes

In this paper we introduce a new experimental approach to determine the potential dependence of the step line tension on metal electrodes in contact with an electrolyte: (0 0 1) and (1 1 n) surfaces of single crystal gold electrodes were investigated by impedance spectroscopy in solutions containing weakly adsorbing anions, such as , F⁻ and . Within the limits of error the shift in the potential of zero charge is proportional to the step density of the vicinal surfaces indicative of a well-defined dipole moment per step length. The dipole moments per step atom are 6.8 ± 0.8, 5.2 ± 0.4, 5.8 ± 0.5 × 10⁻³ eÅ for , , and F⁻ containing electrolytes, respectively. Using the values for the pzc and the potential dependence of the capacitance curves, the potential dependence of the surface tension of the vicinal surfaces is determined. The line tension of the steps is then calculated from the difference between the surface tension of the stepped and the step free surface. Our results represent the first experimental confirmation of a recent theoretical model proposing that in absence of specifically adsorbed ions the step line tension should decrease (roughly linear) with potential.     

Reassignment of the C-Cl stretching frequency in the Ã(A″) state of CBrCl

In a recent theoretical paper, vibrational frequencies were reported for CBrCl in the and à states. These values agree well with our previously published experimental frequencies, except in the case of , where the theoretical value of 968.3 cm⁻¹ is significantly higher than the experimental value of 712.6 cm⁻¹. This discrepancy prompted a re-examination of the assignments for transitions involving ν₁ in the laser induced fluorescence spectrum. If the progression ν₁ + nν₂ has the assignment of n reduced by 1 (the origin is not observed), a new experimental value of results. The close accord with the theoretical value lends weight to this re-assignment. Consequently we propose that the experimental frequency be changed to .