Weighted oscillator strengths and lifetimes for the Si I spectrum

The weighted oscillator strengths (gf) and the lifetimes for Si I presented in this work were carried out in a multiconfiguration Hartree-Fock relativistic approach. In this calculation, the electrostatic parameters were optimized by a least-squares procedure, in order to improve the adjustment to experimental energy levels. This method produces gf-values that are in better agreement with intensity observations and lifetime values that are closer to the experimental ones. In this work we present all the experimentally known electric dipole Si I spectral lines.     

Weighted oscillator strengths and lifetimes for the Si XII and Si XIII spectra

The weighted oscillator strengths (gf) and the lifetimes for Si XII and Si XIII presented in this work were carried out in a multiconfiguration Hartree-Fock relativistic (HFR) approach. In this calculation, the electrostatic parameters were optimized by a least-squares procedure, in order to improve the adjustment to experimental energy levels. This method produces gf-values that are in better agreement with intensity observations and lifetime values that are closer to the experimental ones. In this work we present all the experimentally known electric dipole Si XII and Si XIII spectral lines.     

Weighted oscillator strengths and lifetimes for the S XIV spectrum

The weighted oscillator strengths gf and the lifetimes for S XIV presented in this work have been calculated in a multiconfigurational Hartree–Fock relativistic approach. In this calculation, the electrostatic parameters were optimized by a least-squares procedure in order to improve the adjustment to experimental energy levels. This method produces gf values that are in better agreement with observed line intensities and lifetime values closer to the experimentally determined ones. In this work we presented all the experimentally known electric dipole S XIV spectral lines. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 3, pp. 473–476, 2009.     

Oscillator strengths and lifetimes for the S V spectrum

The semi-empirical weighted oscillator strengths (gf) and the lifetimes presented in this work for all experimentally known electric dipole S V spectral lines and energy levels were carried out in a multiconfiguration Hartree–Fock relativistic (HFR) approach. In this calculation, the electrostatic parameters were optimized by a least-squares procedure, in order to improve the adjustment to experimental energy levels. This method produces lifetime values and gf values that are in agreement with intensity observations used for the interpretation of spectrograms of solar and laboratory plasmas.     

Oscillator strengths and lifetimes for the P XII

Semi-empirical weighted oscillator strengths (gf) and lifetimes presented in this work for all experimentally known electric dipole P XII spectral lines and energy levels were computed within a multiconfiguration Hartree-Fock relativistic approach. In this calculation, the electrostatic parameters were optimized by a leastsquares procedure in order to improve the adjustment to experimental energy levels. The method produces lifetime and gf values that are in agreement with intensity observations used for the interpretation of spectrograms of solar and laboratory plasmas.     

Cu adsorption on pyrite (1 0 0): Ab initio and spectroscopic studies

Surface optimised S 2p photoelectron spectra show that both surface S²⁻ monomers and (S-S)²⁻ dimers are present at pyrite (1 0 0) fracture surfaces. In order to determine which sulfur species are involved in Cu adsorption, fresh pyrite surfaces were exposed to Cu²⁺ in solution. The S 2p spectra suggest that both types of S surface species are involved in the mechanism of Cu adsorption (activation). Ab initio density functional theory was used to model Cu adsorbed onto pyrite (1 0 0) to support the interpretation of the spectroscopy. Mulliken population analysis confirms the charge distribution suggested by the core line shifts as observed in the photoelectron spectra. The ab initio calculations were consistent with a two-coordinate bond between Cu(I), a surface S monomer and a surface S dimer.     

Lifetimes and transition probabilities in Kr V

Weighted oscillator strengths (gf), weighted transition probabilities (gA) and lifetimes are presented for all experimentally known dipole transitions and levels of Kr V. Values were determined by four methods. Three of them are based on the Hartree–Fock method, including relativistic corrections and core-polarization effects, with electrostatic parameters optimized by a least-squares procedure in order to obtain energy levels adjusted to the corresponding experimental values. The fourth method is based on a relativistic multiconfigurational Dirac–Fock approach. In addition, 47 new classified lines belonging to the Kr V spectrum are presented.     

A Monte Carlo simulation study of H2 layers on NaCl(0 0 1)

Monte Carlo simulations show that, at one monolayer coverage, H₂ molecules adsorbed on a NaCl(0 0 1) surface occupy all Na⁺ sites and form a commensurate c(2 × 2) structure. If the Cl⁻ sites are occupied as well, a bi-layer p(2 × 1) structure forms. An examination of the H₂ molecules’ rotational motion shows the molecular axes are azimuthally delocalized and so both of the structures acquire (1 × 1) symmetry in accord with experimental observations. These calculations also show that helicoptering o-H₂ (J = 1, m = ±1) prefer to sit on top of Na⁺ sites, while cartwheeling o-H₂ (J = 1, m = 0) prefers to locate over Cl⁻ sites, in agreement with other work.     

SO2: High-resolution analysis of the (0 3 0), (1 0 1), (1 1 1), (0 0 2) and (2 0 1) vibrational states; determination of equilibrium rotational constants for sulfur dioxide and anharmonic vibrational constants

High resolution Fourier transform spectra of a sample of sulfur dioxide, enriched in ³⁴S (95.3%). were completely analyzed leading to a large set of assigned lines. The experimental levels derived from this set of transitions were fit to within their experimental uncertainties using Watson-type Hamiltonians. Precise band centers, rotational and centrifugal distortion constants were determined. The following band centers in cm⁻¹ were obtained: ν₀(3ν₂)=1538.720198(11), ν₀(ν₁ + ν₃)=2475.828004(29), ν₀(ν₁ + ν₂ + ν₃)=2982.118600(20), ν₀(2ν₃)=2679.800919(35), and ν₀(2ν₁ + ν₃)=3598.773915(38). The rotational constants obtained in this work have been fit together with the rotational constants of lower-lying vibrational states [W.J. Lafferty, J.-M. Flaud, R.L. Sams, EL Hadjiabib, J. Mol. Spectrosc. 252 (2008) 72-76] to obtain equilibrium constants as well as vibration-rotation constants. These equilibrium constants have been fit together with those of ³²S¹⁶O₂ [J.-M. Flaud, W.J. Lafferty, J. Mol. Spectrosc. 16 (1993) 396-402] leading to an improved equilibrium structure. Finally the observed band centers have been fit to obtain anharmonic rotational constants.     

Scattering effects and damping of electrons in Pt(1 1 1) and Cu(1 1 1)

In this work an analysis of experimental and theoretical data associated with the scattering and attenuation of electrons in the Pt(1 1 1) and Cu(1 1 1) crystalline samples is presented. The information about the crystalline structure of the first few atomic layers was obtained by the directional elastic peak electron spectroscopy (DEPES) at the primary electron beam energies E_p from 1.5 keV to 2.0 keV. The comparison of the experimental and theoretical DEPES distributions indicates a qualitative agreement between experiment and theory. The relative signal values associated with the intensity maxima were found to be different. The latter effect suggest that the electron attenuation in the crystalline samples can have an anisotropic character. A qualitative analysis of the characteristic pattern around the [1 1 1] direction concerning the calculation of the scattering factors was performed. The collective scattering of electrons by atoms located around the threefold symmetry axis resulting in the so called ring focusing effect is discussed.     

Structural,electronic and optical properties of CdxZn1 − xS alloys from first-principles calculations

Structural, electronic and optical properties as well as structural phase transitions of ternary alloy Cd_xZn_1 − xS have been investigated using the first-principles calculations based on the density functional theory. We found that the crystal structure of Cd_xZn_1 − xS alloys transforms from wurtzite to zinc blende as Cd content of x=0.83$x=0.83$. Effect of Cd content on electronic structures of Cd_xZn_1 − xS alloys has been studied. The bandgaps of Cd_xZn_1 − xS alloys with wurtzite and zinc blende structures decrease with the increase of Cd content. Furthermore, dielectric constant and absorption coefficient also have been discussed in detail.     

Formation of vinylidene and vinylene by selective reactivity of Si(1 0 0)2 × 1 towards iso, cis and trans isomers of dichloroethylene

The room temperature (RT) chemisorption of three (iso, cis and trans) isomers of dichloroethylene (DCE) on Si(1 0 0)2 × 1 have been investigated by X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD). Unlike ethylene, the lack of molecular desorption features in the TPD data effectively rules out the cycloaddition adsorption mechanism for all three isomers. XPS spectra show that cis- and trans-DCE adsorb dissociatively on the 2 × 1 surface in equal proportion as mono-σ bonded 2-chlorovinyl and di-σ bonded vinylene adspecies, which could be produced by dechlorination mechanisms involving the proposed tri-atom π-complex and diradical intermediates, respectively. Acetylene (m/z 26) evolution from 2-chlorovinyl adspecies at 590 K and vinylene at 750 K are also observed for both cis- and trans-DCE, further confirming the common adsorption mechanisms for these geometrical isomers and the relative stabilities of the adspecies. In contrast, only vinylidene adspecies is found for iso-DCE, which indicates that the high ionicity of the CCl₂ group favours the diradical dechlorination mechanism. The single m/z 26 desorption peak for iso-DCE adspecies observed at a higher temperature (780 K) than cis and trans isomers is consistent with the higher adsorption energy of vinylidene than vinylene on Si(1 0 0) obtained in our ab initio calculations. The different relative locations of the Cl atoms in these isomers therefore play a crucial role in controlling the adsorption and thermal evolution on Si(1 0 0)2 × 1. The selective reactivity of the 2 × 1 surface towards these isomers can be used to generate vinylene or vinylidene templates from their corresponding adspecies.     

Kinetics of the H + NCO reaction

Ab initio transition state theory (TST) based master equation simulations are used to predict the temperature and pressure dependence of the H + NCO reaction rate and product branching. The barrierless entrance channels to form singlet HNCO and NCOH are studied with variable reaction coordinate TST employing a potential energy surface obtained from multi-reference configuration interaction ab initio calculations. The remaining channels, including reactions on the triplet surface, are studied with standard TST methods employing high level electronic structure results. The energy transfer parameters for the master equation simulations arise from a fit to the experimentally observed HNCO dissociation rate. The lowest energy threshold to formation of bimolecular products, ³NH + CO, lies well below the reactants. The bottleneck for intersystem crossing, which precedes the formation of ³NH + CO from the singlet adducts, becomes the dominant bottleneck for that channel at quite low energies relative to reactants. The effect of this bottleneck is studied with model calculations designed to reproduce detailed experimental observations of photolysis branching ratios. This bottleneck greatly reduces the flux from H + NCO to ³NH + CO via the singlet adducts. As a result, stabilization and reaction on solely the triplet surface are significant components of the overall rate. The present predictions for the high pressure and collisionless limit rate coefficients are accurately reproduced over the 200-2500 K range by the expressions, 1.53 × 10⁻⁵T^−1.86exp(−399/T) + 1.07 × 10³T^−3.15exp(−15219/T) and 5.62 × 10⁻¹²T^0.493exp(148/T) cm³ molecule⁻¹ s⁻¹, respectively, where T is in K. These predictions are in reasonably satisfactory agreement with the somewhat discordant experimental rate measurements.     

A perturbation theory study of H2 on LiF(0 0 1)

In response to recent helium atom scattering (HAS) results, Monte Carlo (MC) simulations and perturbation theory have been performed for H₂ on LiF(0 0 1). MC simulations predict that H₂ molecules form a series of structures, p(2 × 2), p(8 × 2), p(4 × 2) with coverages Θ = 0.5, 0.625 and 0.75, respectively, that are stable up to 8 K. This is in partial agreement with the HAS results that report c(2 × 2) and c(8 × 2) structures; they agree in terms of coverage and stability, but disagree in terms of symmetry. To reconcile the results of the simulations and experiments, the orientation of the adsorbed H₂ molecules was studied using perturbation theory. These calculations show that the adsorbed H₂ molecules are azimuthally delocalized and that the structures are c-type rather then p-type. The calculations also indicate that p-H₂ and helicoptering o-H₂ prefer cationic sites, while cartwheeling o-H₂ prefers anionic sites.     

Analysis of the rotational spectrum of pyruvonitrile up to 324 GHz

The room-temperature rotational spectrum of pyruvonitrile (acetyl cyanide, CH₃COCN) was measured up to 324 GHz, and additional measurements were also made in supersonic expansion in the region 7-19 GHz. The available data sets for the A and E torsional sublevels were extended to over 1200 transitions, J = 65 and K_a = 38 for the ground vibrational state, and to comparable numbers of transitions for first excited states of the methyl torsional mode ν₁₈, and the in-plane CCN bending mode ν₁₂. The collected experimental measurements were fitted with several different computer programs for dealing with the effects of methyl torsional motion on the rotational spectrum and many spectroscopic constants have been determined. The experimental results are discussed in detail and are augmented by ab initio computations. Stark effect measurements in supersonic expansion were used to precisely determine the electric dipole moment of pyruvonitrile, ∣μ_a∣ = 2.462(2) D, ∣μ_b∣ = 2.442(2) D, μ_tot = 3.468(2) D. Pyruvonitrile, as an 8-atom molecule with a sizable dipole moment, is a possible candidate for astrophysical detection and the present work provides the laboratory data necessary for that purpose.     

Polarization maintaining holey fibers for residual dispersion compensation over S + C + L wavelength bands

We report on a highly birefringent holey fiber for broadband dispersion compensation covering the S, C, and L telecommunication bands i.e. wavelength ranging from 1460 to 1625 nm. The finite element method with circular perfectly matched layer boundary condition is used to investigate the guiding properties. Numerical analysis demonstrates that it is possible to obtain negative dispersion coefficient of about −470 to −850 ps/nm/km over S to L-bands and a relative dispersion slope perfectly matched with single mode fiber (SMF) of about 0.0036 nm⁻¹ at 1550 nm. At the same time birefringence of the order 2.53 × 10⁻² is realized at 1550 nm wavelength. Owing to superior optical properties of the proposed holey fiber, this can be a promising candidate for broadband dispersion compensation and sensing applications.     

Adsorption of iso-butane on ZnO(0 0 0 1)-Zn

Presented are thermal desorption spectroscopy (TDS) and adsorption probability measurements of iso-butane on the Zn-terminated surface of ZnO. The initial adsorption probability, S₀, decreases linearly from 0.57 to 0.22 (±0.02) with impact energy, E_i = 0.74-1.92 eV, and is independent of adsorption temperature, T_s = 91-114 K (±5 K), indicating non-activated molecular adsorption. The coverage, Θ, dependent adsorption probabilities, S(Θ), show a cross-over from adsorbate-assisted adsorption (S increases with Θ) to Kisliuk-like dynamics at about the desorption temperature of iso-butane bi-layers (∼110 K). Thus, the adsorption dynamics are precursor-mediated. The enhanced (gas-surface) mass-match, caused by forming a second layer of the alkane, leads to adsorbate-assisted adsorption. A direct fitting procedure of the TDS data yields a pre-exponential factor of 2.5 × 10¹³/s and a coverage dependent heat of adsorption of E_d(Θ) = 39 − 6 ∗ Θ + 2.5 ∗ exp(−Θ/0.07) kJ/mol.     

Thermodynamic investigations of ternary o-toluidine + tetrahydropyran + N,N-dimethylformamide mixture and its binaries at 298.15, 303.15 and 308.15 K

The densities ρ, speed of sound u, data of o-toluidine (i) + tetrahydropyran (j) + N,N-dimethylformamide (k) and its {tetrahydropyran (j) + N,N-dimethylformamide (k); o-toluidine (i) + N,N-dimethylformamide (k)} binaries have been measured as a function of composition at 298.15, 303.15 and 308.15 K. The excess molar enthalpies, H^E data of same set of binary mixtures have also been measured over entire composition at 308.15 K. The densities and speeds of sound data of binary and ternary mixtures have been utilized to determine their excess molar volumes, V^E and excess isentropic compressibilities, κ_S^E. The observed thermodynamic properties of binary and ternary mixtures have been analyzed in terms of Graph theory. It has been observed that Graph theory correctly predicts the sign as well as magnitude of thermodynamic properties.     

The magnetic map of NiMn alloy thin films on Co(0 0 1) and Co(1 1 1)

Following the experimental work of Groudeva-Zotova et al. [S. Groudeva-Zotova, D. Elefant, R. Kaltofen, D. Tietjen, J. Thomas, V. Hoffmann, C.M. Schneider, J. Magn. Magn. Mater. 263 (2003) 57] where the magnetic and structural characteristics of a bi-layer NiMn-Co exchange biasing systems was investigated, density functional calculations with generalized gradient corrections were performed on (Mn_0.5Ni_0.5)_n ordered alloy on Co(0 0 1) and one Mn_1−xNi_x monolayer on Co(1 1 1). For the Mn_0.5Ni_0.5 monolayer on Co(0 0 1), magnetic moments per surface atom of 0.65 μ_B and 3.76 μ_B were obtained for Ni and Mn, respectively. Those magnetic moments are aligned parallel to the total moment of Co(0 0 1). A complex behavior of the Mn moment in dependence of the thickness “n” is obtained for (Mn_0.5Ni_0.5)_n on Co(0 0 1). Investigations on Mn_1−xNi_x monolayer on Co(1 1 1) have shown that the crystallographic orientation does not modify significantly neither the magnetic moments of Mn and Ni atoms nor their ferromagnetic coupling with the Co(1 1 1) substrate, except for x = 0.66. For x = 0.66 the Mn sub-lattice presents an antiferromagnetic coupling leading to a quenching of the Ni magnetic moment.     

CF interaction with Si(1 0 0)-(2 × 1): Molecular dynamics simulation

In this study, the interaction of CF with the clean Si(1 0 0)-(2 × 1) surface at normal incidence and room temperature was investigated using molecular dynamics simulation. Incident energies of 2, 12 and 50 eV were simulated. C atoms, arising from dissociation, preferentially react with Si to form Si-C bonds. A Si_xC_yF_z interfacial layer is formed, but no etching is observed. The interfacial layer thickness increases with increasing incident energy, mainly through enhanced penetration of the silicon lattice. Silicon carbide and fluorosilyl species are formed at 50 eV, which is in good agreement with available experimental data. The level of agreement between the simulated and experimental results is discussed.