High resolution analysis of the rotational levels of the (0 0 0), (0 1 0), (1 0 0), (0 0 1), (0 2 0), (1 1 0) and (0 1 1) vibrational states of SO2

A high resolution (0.0018 cm⁻¹) Fourier transform instrument has been used to record the spectrum of an enriched ³⁴S (95.3%) sample of sulfur dioxide. A thorough analysis of the ν₂, 2ν₂ − ν₂, ν₁, ν₁ + ν₂ − ν₂, ν₃, ν₂ + ν₃ − ν₂, ν₁ + ν₂ and ν₂ + ν₃ bands has been carried out leading to a large set of assigned lines. From these lines ground state combination differences were obtained and fit together with the existing microwave, millimeter, and terahertz rotational lines. An improved set of ground state rotational constants were obtained. Next, the upper state rotational levels were fit. For the (0 1 0), (1 1 0) and (0 1 1) states, a simple Watson-type Hamiltonian sufficed. However, it was necessary to include explicitly interacting terms in the Hamiltonian matrix in order to fit the rotational levels of the (0 2 0), (1 0 0) and (1 0 1) states to within their experimental accuracy. More explicitly, it was necessary to use a ΔK = 2 term to model the Fermi interaction between the (0 2 0) and (1 0 0) levels and a ΔK = 3 term to model the Coriolis interaction between the (1 0 0) and (0 0 1) levels. Precise Hamiltonian constants were derived for the (0 0 0), (0 1 0), (1 0 0), (0 0 1), (0 2 0), (1 1 0) and (0 1 1) vibrational states.     

High-Resolution Infrared Spectrum of CD(3)CN: Analysis of the Interacting nu(3) and nu(6) Bands and Evaluation of the A(0) Constant

The infrared spectrum in the range 900-1230 cm(-1) including the fundamental bands nu(3) and nu(6) of CD(3)CN has been studied. The resolution attained was 0.0025 cm(-1) in the measurement on the Bruker 120 HR Fourier spectrometer in Oulu. About 4000 lines were assigned in the nu(6) band. For the weak nu(3) band, which has not been observed earlier directly, we were able to assign 206 lines in three subbands K=8-10. These lines become detectable due to the strong nu(3)/nu(6) Coriolis resonance. There is also an l(1,-2) resonance between nu(3) and nu(6), which made it possible to obtain a value 2.647721(50) cm(-1) for the axial rotational constant A(0), when D(0)(K) from force field calculations was applied. Different types of resonances with the overtone 3nu(8) and the combinations nu(4)+nu(8) and nu(7)+nu(8) were observed. A fit with a standard deviation of 0.0019 cm(-1) was attained by using a model of 10 different resonances. Copyright 2001 Academic Press.     

CO oxidation on Pd(1 1 1), Pt(1 1 1), and Rh(1 1 1) surfaces studied by infrared chemiluminescence spectroscopy

The infrared (IR) chemiluminescence studies of CO₂ formed during steady-state CO oxidation over Pd(1 1 1), Pt(1 1 1), and Rh(1 1 1) surfaces were carried out. Analysis of their emission spectra indicates that the order of the average vibrational temperature () values of CO₂ formed during CO oxidation was as follows: Pd(1 1 1) > Pt(1 1 1) > Rh(1 1 1), and the order is coincident with the potential energy in the transition state expected by the theoretical calculations. Furthermore, it is suggested that the bending vibrational temperature () can also be influenced by the angle of O-C-O (∠_OCO) of the activated complex in the transition state, which has also been proposed by the theoretical calculations.     

High-resolution infrared and subterahertz spectroscopy of the v2 = 1, v5 = 1, and v3 = 2 levels of CH3Cl

High-resolution Fourier-transform infrared spectra between 1235 and 1680 cm⁻¹ and subterahertz spectra between 250 and 630 GHz of monoisotopic ¹³CH₃³⁵Cl have been recorded and analyzed simultaneously, with all Coriolis, α-resonance, and l-type interactions in the polyad of the v₂ = 1, v₅ = 1, and v₃ = 2 levels taken into account. Several α-resonances (Δk = ±2, Δl = ?1) generating perturbation-allowed transitions have been assigned in the rovibrational spectra. These resonances enabled us to determine accurately and independently the ground state rotational and centrifugal distortion parameters A₀ = 5.205 746 9 (55) cm⁻¹ and . Even , which is, however, correlated to higher-order α-resonance terms, was determined. With 51 upper state parameters varied, about 5800 rovibrational wavenumbers and more than 550 rotational frequencies pertaining to the excited vibrational states were fitted within their experimental accuracy.     

NO dissociation pathways on Rh(1 0 0), (1 1 0), and (1 1 1) surfaces: A comparative density functional theory study

The chemisorption and dissociation pathways of NO on the Rh(1 0 0), (1 1 0), and (1 1 1) surfaces are studied by the plane-wave density functional theory (DFT) with CASTEP program. In addition, the electronic and geometrical effects that affect the NO dissociation reactions have been investigated in detail. The calculation results are presented as following: The effective activation energies of the best NO dissociation pathways on the Rh(1 0 0), the Rh(1 1 0), and the Rh(1 1 1) are 0.63, 0.66 and 1.77 eV, respectively. The activity of the Rh planes for NO dissociation is in the order of Rh(1 0 0) ≈ Rh(1 1 0) > Rh(1 1 1). The low dissociation barrier for Rh(1 0 0) and Rh(1 1 0) is associated with the existence of a lying-down NO structure which acts as a precursor for dissociation. By Mulliken population analysis and structure analysis, both electronic and geometrical effects are found to affect the NO dissociation reactions, but the geometrical effect exceed the electronic. The energy decomposition scheme has been used to provide further insight into the NO dissociation reactions. Based on the calculations, the interaction energy between N and O in the transition state on the Rh(1 1 1) is found much larger than that on the Rh(1 0 0) and the Rh(1 1 0). The major differences of should originate from the variation of the bonding competition effect.     

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.     

Mass and lattice effects in trapping: Ar, Kr, and Xe on Pt(1 1 1), Pd(1 1 1), and Ni(1 1 1)

The trapping probabilities of argon, krypton, and xenon on Pd(1 1 1) and Ni(1 1 1) have been investigated using supersonic molecular beam techniques. The trapping probability of argon exhibits normal incident energy in a similar fashion on both Pd(1 1 1) and Pt(1 1 1) because the mass of argon is significantly less than the surface mass of either Pd or Pt. In contrast, dynamic corrugation in the gas-surface potential is observed for krypton trapping on Pt(1 1 1) and Pd(1 1 1), resulting in a decreased angular dependence of the trapping probability compared to argon. For xenon trapping on Pd significant lattice deformation during the gas-surface collision appears to give rise to total energy scaling. The trapping probability of xenon on Pd(1 1 1) remains high at unusually high incident kinetic energies due to the overall enhanced energy transfer from the incident atom to the lattice. Trapping probabilities of Ar, Kr, and Xe are significantly lower on Ni(1 1 1) than on either Pt(1 1 1) or Pd(1 1 1) despite the lower surface mass of the Ni atoms. This result is attributed to the lower binding energy of the rare gases on Ni(1 1 1) and the higher Debye temperature of Ni. The energy scaling of Ar trapping on Ni(1 1 1) is determined by static corrugation, but the energy scaling for Kr and Xe on Ni(1 1 1) may involve the effects of dynamic corrugation. In the latter cases, the greater stiffness of the nickel lattice decreases the dynamic corrugation relative to Pt(1 1 1) and Pd(1 1 1).     

High resolution analysis of the ν12 and ν17 fundamental bands of acrolein, CH2CHCHO, in the 600 cm region

Synchrotron radiation from the new Canadian Light Source facility has been used to obtain a high resolution (0.0012 cm⁻¹) absorption spectrum of acrolein vapor in the 550-660 cm⁻¹ region. Almost 2000 transitions have been included in a detailed analysis of the ν₁₂ (∼564 cm⁻¹) and ν₁₇ (∼593 cm⁻¹) fundamental bands which yielded precise values for the band origins, rotational and centrifugal distortion parameters. The analysis included the a- and b-type Coriolis interactions connecting ν₁₂ and ν₁₇, as well as an a-type Coriolis interaction between ν₁₇ and a “dark” perturbing state, identified as 4ν₁₈. We believe that this is the first high resolution infrared study of acrolein.     

Infra-red absorption bands 1-0, 2-0, 3-0 and 4-0 of the two isotopic species D79Br and D81Br of deuterium bromide

High resolution spectra of the 1-0, 2-0, 3-0, and 4-0 infra-red absorption bands of the two isotopic species of deuterium bromide have been recorded up to very high J values. The equilibrium molecular parameters obtained in the analysis fit the 267 observed lines within their experimental uncertainties, and give precise calculated wavenumbers for some observed chemical laser lines of these molecules.     

Improved measurements and analysis of the far-infrared spectrum of methanol-D1 (CH2DOH) arising from trans- (e0) to gauche- (e1 & o1) states

In this work the millimeter-wave (MMW) and far infrared (FIR) absorption spectrum for the asymmetrically deuterated Methanol (CH₂DOH) species measured recently at a temperature of −60 °C with better accuracy and signal/noise (S/N) ratio than known before has been assigned for transitions originating at the lowest lying trans- to gauche-states. The entire spectrum for 50–1200 cm⁻¹ has been re-recorded recently using the Synchrotron Radiation Source coupled with the Bruker Fourier Transform Infrared (FTIR) spectrometer with a resolution of about 0.001 cm⁻¹ or better. Complete spectrum has not been exploited a great deal but it helped to entangle overlapping lines in the present work. This also fills the gap remaining in the usual FTIR in the range 400–500 cm⁻¹. Hence it is expected to help the interacting partner for the Coriolis interaction encountered earlier. The assigned transitions mostly for the axial rotational angular momentum quantum number K + 1 ← K, both for R- and Q-sub bands for wide range of rotational angular momentum quantum number. The MMW spectrum has been recalibrated and assigned for a number of Q-branches. The assignments are confirmed rigorously using closed loop residual technique. The assigned ^rR and ^rQ lines have been analyzed in terms of polynomial expansion parameters. The new assignments are presented for about 750 transitions and a grand atlas of more than 1000 lines has been prepared which will be made available through the open source server at “research gate”. The present work should be useful in the area of astrophysical detection and further understanding of the energy relaxation pathways in the molecule.     

Fabrication of nanostructures on Si(1 0 0) and GaAs(1 0 0) by local anodic oxidation

Atomic force microscopes have become useful tools not only for observing surface morphology and nanostructure topography but also for fabrication of various nanostructures itself. In this paper, the application of AFM for fabrication of nanostructures by local anodic oxidation (LAO) of Si(1 0 0) and GaAs(1 0 0) surfaces is presented. A special attention is paid to finding relations between the size of oxide nanolines (height and half-width) and operational parameters as tip-sample voltage and tip writing speed. It was demonstrated that the formation of silicon oxide lines obeys the Cabrera-Mott theory, i.e. the height of the lines grow, linearly with tip-sample voltage and is inversely proportional to logarithm of tip writing speed. As for GaAs substrates, the oxide line height grows linearly with tip-sample voltage as well but LAO exhibits a certain deviation from this theory. It is shown that the selective chemical etching of Si or GaAs ultrathin films processed by LAO makes it possible to use these films as nanolithographic masks for further nanotechnologies, e.g. fabrication of metallic nanostructures by ion-beam bombardment. The ability to control LAO and tip motion can be utilized in fabrication of complex nanostructures finding their applications in nanoelectronic devices, nanophotonics and other high-tech areas.     

Reflection absorption infrared study of the adsorption of dimethylamine on copper (1 1 0) and nickel (1 1 1) surfaces

The adsorption of dimethylamine on Cu(1 1 0) and Ni(1 1 1) has been studied by reflection absorption infrared spectroscopy. For Cu(1 1 0), adsorption was molecular at 80 and 300 K and for submonolayer dimethylamine the appearance of A′ and not A″ modes indicated C_s symmetry. Similar bonding was found for Ni(1 1 1) at 170 K. Annealing the adlayer to 350 K resulted in the formation of a new species on Ni(1 1 1), similar to that which has been identified as methylaminocarbyne on Pt(1 1 1). In contrast only molecular dimethylamine was identified on Cu(1 1 0), with H-bonded interactions at high coverage and a potential surface dimer.     

First principle study of SrTiO3 (0 0 1) surface and adsorption of NO on SrTiO3 (0 0 1)

The results of first-principles calculations about the two possible terminations of (0 0 1) surface of SrTiO₃ perovskite and adsorption of NO on SrTiO₃ (0 0 1) surface were presented. Both surface parameters (atomic structures and electronic configurations) and adsorption parameters (bond, energy and charge) of NO on SrTiO₃ (0 0 1) surface, which have never been investigated before as far as we know were investigated using density functional theory calculations with the local-density approximation (DFT-LDA). It was found that the two possible terminations of SrTiO₃ (0 0 1) surface have large surface relaxation, which leads to surface polarization and exhibits different reactivity toward the dissociative adsorption of NO. The electronic states of TiO₂-terminated surface have larger difference than that of bulk, so it is more favorable for adsorption of NO than SrO-terminated surface.     

Analysis of the first triad of interacting states (0 2 0), (1 0 0), and (0 0 1) of D2O from hot emission spectra

The far-infrared and middle-infrared emission spectra of deuterated water vapour were measured at temperatures 1370, 1520, and 1940 K in the ranges 320-860 and 1750-3400 cm⁻¹. The measurements were performed in an alumina cell with an effective length of hot gas of about 50 cm. More than 3550 new measured lines for the D₂¹⁶O molecule corresponding to transitions from highly excited rotational levels of the (0 2 0), (1 0 0), and (0 0 1) vibrational states are reported. These new lines correspond to rotational states with higher values of the rotational quantum numbers compared to previously published determinations: J_max = 29 and K_a(max) = 22 for the (0 2 0) state, J_max = 29 and K_a(max) = 25 for the (1 0 0) state, and J_max = 30 and K_a(max) = 23 for the (0 0 1) state. The extended set of 1987 experimental rotational energy levels for the (0 2 0), (1 0 0), and (0 0 1) vibration states including all previously available data has been determined. For the data reduction we used the generating function model. The root mean square (RMS) deviation between observed and calculated values is 0.004 cm⁻¹ for 1952 rovibrational levels of all three vibration states. A comparison of the observed energy levels with the best available values from the literature and with the global predictions from molecular electronic potential energy surfaces of water isotopic species [H. Partridge, D.W. Schwenke, J. Chem. Phys. 106 (1997) 4618] is discussed. The latter confirms a good consistency of mass-dependent DBOC corrections in the PS potential function with new experimental rovibrational data.     

Computational study of cycloaddition reactions on the SiC(1 0 0)-c(2 × 2) surface

Cycloaddition reactions between 1,3-butadiene and the C-terminated SiC(1 0 0)-c(2 × 2) surface have been addressed using quantum-chemical methods. The c(2 × 2) structure consists of ---CC--- bridges between underlayer Si atoms which themselves form Si---Si bonds. Of various possible reaction products, the one formed by a [2 + 4] reaction with the ---CC--- bridge (giving a species resembling 1,4-cyclohexadiene) is the lowest in energy. Density functional calculations for the bare c(2 × 2) surface, using a cluster model with mechanical embedding, gave good agreement with structural parameters obtained in previous fully ab initio studies. Similar calculations for the cycloaddition product and for the transition state gave a reaction energy of −50.3 kcal/mol and an activation energy of +6.1 kcal/mol to form a planar ring structure lying normal to the surface. Detailed results for the frequency and infrared polarization behavior of adsorbate vibrational modes have also been obtained.     

Surface investigation of Si(1 0 0), Cu, Cu on Si(1 0 0), and Au on Cu with positron annihilation induced Auger-electron spectroscopy

The surfaces of polycrystalline Cu, Au-coated Cu, Si(1 0 0) and of Si(1 0 0) coated with 1.5 monolayer Cu were investigated with positron annihilation induced Auger-electron spectroscopy (PAES). Since the electron background has been reduced considerably we observed the Cu M_2,3VV-Auger transition on a copper surface within only three hours which is the shortest acquisition time reported so far for PAES. In order to demonstrate PAES’ high potential the Auger-yield, the signal-to-background ratio as well as the surface selectivity were compared with accompanying EAES-measurements quantitatively. A more efficient electron energy analyzer for the present PAES setup would lead to an additional efficiency gain of more than two orders of magnitude. The presented measurements were performed at the low-energy positron beam of high intensity NEPOMUC at the research reactor FRM II.     

High-Resolution Infrared, Microwave, and Submillimeter-Wave Study of FClO(2) in the nu(2), nu(3), nu(4), and nu(6) Excited States

A high-resolution analysis of the {nu(2), nu(3)} and {nu(4), nu(6)} bands of the two isotopomers of chloryl fluoride F(35)ClO(2) and F(37)ClO(2) has been carried out for the first time using simultaneously infrared spectra recorded around 16&mgr;m and 26&mgr;m with a resolution of ca. 0.003 cm(-1) and microwave and submillimeter-wave transitions occurring within the vibrational states 2(1), 3(1), 4(1), and 6(1). Taking into account the Coriolis resonances which link the rotational levels of the {2(1), 3(1)} and the {4(1), 6(1)} interacting states, it was possible to reproduce very satisfactorily the observed transitions and to determine accurate vibrational energies and rotational constants for the upper states 2(1), 3(1), 4(1), and 6(1) of both the (35)Cl and (37)Cl isotopic species. Copyright 2001 Academic Press.     

Spin excitations in exchange-dominated regime on (1 0 0) and (1 1 0) antiferromagnetic surfaces

Theoretical investigations in the context of Heisenberg model have been made for (1 0 0) and (1 1 0) magnetic surface dynamics for a semi-infinite antiferromagnet geometry. The calculations apply to the exchange dominated regime and are based on a spin-wave operator and matching technique within the framework of non-interacting spin-wave theory. The theoretical formalism developed here does not include either relaxation or reconstruction at the surface and no electronic effects have been considered. Dispersion curves of surface spin-waves are obtained within a single framework by matching the evanescent and travelling solutions, respectively, obtained from the secular equation and satisfying the boundary conditions brought about by the surface. The excitation spectrum of the surface spin-waves has been obtained and compared with that for bulk spin-waves. The quantized bulk modes of the same energy travelling to and away from the surface are related to one another by reflection coefficients, for which sum rules are derived. The numerical results for the evolution of acoustic and optical modes are presented for two different surface planes, namely (1 0 0) and (1 1 0). The findings reported here show that: (i) the reduced coordination number for atoms near the surface as well as the surface orientation play an obvious and crucial part in the surface spin-wave spectra; (ii) the evolutions of bulk as well as surface modes undergo significant changes as a function of the bulk-surface exchange integrals for a given direction of propagation of the spin-wave modes along the surface.     

Accurate rotational spectroscopy of sulfur dioxide, SO2, in its ground vibrational and first excited bending states, v2 = 0, 1, up to 2 THz

Approximately 150 pure rotational transitions each have been recorded for SO₂, v₂ = 0 and 1, in selected frequency regions up to 2 THz. The J and K_a quantum numbers reach very high values: 92 and 23, respectively, for the ground vibrational state and 81 and 21, respectively, for the first excited bending state. The highest levels accessed are almost 3000 cm⁻¹ above ground. The relative experimental uncertainties Δν/ν are about 10⁻⁸ for several medium to strong, isolated lines, and generally better than 2.5 × 10⁻⁷. Improved spectroscopic parameters have been obtained for both states, particularly for the excited bending state. In fact, the accuracies with which the energy levels of the v₂ = 1 state are known depend essentially only on the accuracy with which the vibrational spacing is known from infrared spectroscopy.     

Solvent effects on adsorption of CO over CuCl(1 1 1) surface: A density functional theory study

DFT calculations have been performed to investigate the effect of dielectric responses of the solvent environment on the CO adsorption over CuCl(1 1 1) surface by using COSMO (conductor-like solvent model) model in Dmol³. Different dielectric constants, including vacuum, liquid paraffin, methylene chloride, methanol and water solution, are considered. The effects of solvent model on the structural parameters, adsorption energies and vibrational frequency of CO adsorption over CuCl(1 1 1) surface have been investigated. The calculation results suggest that solvent effects can improve the stability of CO adsorption and reduce the intensity of C-O bond, which might mean that solvent is in favor of C-O bond activation and improve the reaction activity of oxidative carbonylation in a slurry reactor.