The CΠu state of Na2 revisited: A comprehensive study by polarization labeling spectroscopy technique

This paper contains the analysis of the C(2)¹Π_u state of Na₂ molecule based on a large data set (3030 lines) obtained from a polarization labeling spectroscopy experiment on the transition. The energies of rovibrational levels in the C state, spanning a wide range of v (0 ? v ? 43) and J (12 ? J ? 100) quantum numbers, are fitted to a Dunham polynomial expansion and also to a numerical potential curve constructed by the inverted perturbation approach (IPA) method.     

Epitaxial growth of ultra-thin NiO films on Cu(1 1 1)

The very first stages of the growth of NiO on Cu(1 1 1) is examined on a microscopic scale. The paper focuses on the morphological and structural characterization of nanostructures formed in the 0-1 Å thickness range. Ultra-thin NiO films, obtained through evaporation of a Ni rod under an oxygen atmosphere were grown at 550 K. In the early stages of the growth the oxide film morphology shows 10-30 nm large, monolayer high, islands with a partial incorporation of metallic Ni in the first Cu(1 1 1) surface plane. The first layer is formed by an epitaxial atomic layer exhibiting a STM contrast similar to the one observed on adsorbed oxygen on Cu(1 1 0). A NiO cluster nucleation and coalescence mechanism is proposed in order to explain the formation of the second NiO layer. A α-Ni₂O₃ hexagonal phase, or a structural distortion of the NiO(1 1 1)()R30° structure could both explain the complex LEED patterns.     

Rotational levels of the (0 0 0) and (0 1 0) states of D2O from hot emission spectra in the 320-860 cm region

The far-infrared emission spectra of deuterated water vapour were measured at different temperatures (1370, 1520, and 1950 K) in the range 320-860 cm⁻¹ at a resolution of 0.0055 cm⁻¹. The measurements were performed in an alumina cell with an effective length of hot gas of about 50 cm. More than 1150 new measured lines for the D₂¹⁶O molecule corresponding to transitions between highly excited rotational levels of the (0 0 0) and (0 1 0) 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=26 and for the (0 0 0) ← (0 0 0) band, J_max=25 and for the (0 1 0) ← (0 1 0) band, and J_max=26 and for the (0 1 0) ← (0 0 0) band. The estimated accuracy of the measured line positions is 0.0005 cm⁻¹. To our knowledge no experimentally measured rotational transitions for D₂¹⁶O within an excited vibrational state have been available in the literature so far. An extended set of experimental rotational energy levels for (0 0 0) and (0 1 0) 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 0.0012 cm⁻¹ for 692 rotational levels of the (0 0 0) state and 0.0010 cm⁻¹ for 639 rotational levels of the (0 1 0) vibrational state. 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 surface [J. Chem. Phys. 106 (1997) 4618] for the (0 0 0) and (0 1 0) states is discussed.     

The 2ν4 overtone bands of FClO3

The high resolution infrared spectrum of the mono-isotopic species F³⁵Cl¹⁶O₃ has been studied in the region of the 2ν₄ overtone, from 2560 to 2680 cm⁻¹. The perpendicular component is strong and clearly observed while the parallel component is very weak and almost completely hidden by the perpendicular one. Their origins differ by 12.6 cm⁻¹, the being located at higher wavenumbers. The band is perturbed by the anharmonic interaction between the v₄ = 2, l₄ = ?2 and v₂ = v₄ = v₅ = 1, l₄ = l₅ = ±1 excited states, both of E symmetry. In total 3157 transitions have been assigned, 83% of these to , 12% to , and 5% to . The three bands have been analyzed simultaneously, taking into account the Fermi resonance effective between the excited states of E symmetry. The ro-vibration parameters of the excited states have been obtained, including the deperturbed band origins of and , at 2628.5890(4) and 2619.3342(5) cm⁻¹, respectively. The W₂₄₅ anharmonic constant is equal to 4.0161(4) cm⁻¹. The x₄₄+g₄₄ and x₂₄+x₄₅+g₄₅ anharmonicity constants have been derived from the obtained band origins and those of ν₄ and ν₂ + ν₅.     

Equilibrium structure in the presence of internal rotation: A case study of cis-methyl formate

The Born-Oppenheimer (BO) equilibrium molecular structure () of cis-methyl formate has been determined at the CCSD(T) level of electronic structure theory using Gaussian basis sets of at least quadruple-ζ quality and a core correlation correction. The quadratic, cubic and semi-diagonal quartic force field in normal coordinates has also been computed at the MP2 level employing a basis set of triple-ζ quality. A semi-experimental equilibrium structure () has been derived from experimental ground-state rotational constants and the lowest-order rovibrational interaction parameters calculated from the ab initio cubic force field. To determine structures, it is important to start from accurate ground-state rotational constants. Different spectroscopic methods, applicable in the presence of internal rotation and used in the literature to obtain “unperturbed” rotational constants from the analysis and fitting of the spectrum, are reviewed and compared. They are shown to be compatible though their precision may be different. The and structures are in good agreement showing that, in the particular case of cis-methyl formate, the methyl torsion can still be treated as a small-amplitude vibration. The best equilibrium structure obtained for cis-methyl formate is: r(C_m-O) = 1.434 Å, r(O-C_c) = 1.335 Å, r(C_m-H_s) = 1.083 Å, r(C_m-H_a) = 1.087 Å, r(C_c-H) = 1.093 Å, r(CO) = 1.201 Å, ∠(COC) = 114.4°, ∠(CCH_s) = 105.6°, ∠(CCH_a) = 110.2°, ∠(OCH) = 109.6°, ∠(OCO) = 125.5°, and τ(H_aCOC) = 60.3°. The accuracy is believed to be about 0.001 Å for the bond lengths and 0.1° for the angles.     

Experimental and theoretical studies on X-ray induced secondary electron yields in Ti and TiO2

Generation of X-ray induced secondary electrons in Ti and TiO₂ was studied from both experimental and theoretical approaches, using X-ray photoelectron spectroscopy (XPS) attached to a synchrotron radiation facility and Monte Carlo simulation, respectively.The experiment revealed that the yields of secondary electrons induced by X-rays (electrons/photon) at photon energies to 4950 and 5000 eV for Ti and TiO₂ are δ_Ti(4950 eV) = 0.002 and δ_Ti(5000 eV) = 0.014 while those for TiO₂ are δTiO₂(4950 eV)=0.003 and δTiO₂(5000 eV)=0.018.A novel approach to obtain the escape depth of secondary electrons has been proposed and applied to Ti and TiO₂. The approach agreed very well with the experimental data reported so far. The Monte Carlo simulation predicted; and while and .An experimental examination on the contribution of X-ray induced secondary electrons to photocatalysis in TiO₂ has also been proposed.     

Σu and Πu states of the hydrogen molecule: Nonadiabatic couplings and vibrational levels

Nonadiabatic coupling matrix elements are computed for six lowest and four lowest ¹Π_u electronic states of H₂ in a wide range of internuclear distances. These matrix elements are used together with the adiabatic potentials to determine the bound ro-vibrational levels of the 10 electronic states for rotational quantum numbers J ? 10. The computed energies agree quite well with existing experimental term values. However, some of the experimental levels should be assigned differently.     

A visible spectrum of jet-cooled rhodium monosulfide

The diatomic molecule RhS has been observed for the first time. It has been studied by high resolution laser-induced fluorescence spectroscopy in a supersonic molecular beam following reaction by laser-vaporized rhodium atoms with CS₂ doped in He. Electronic, vibrational, and rotational data have been collected. The RhS ground state has ⁴Σ⁻ symmetry with a second-order spin-orbit splitting of 47.43 cm⁻¹, indicating case (a) coupling at low J. Three bands in the 535-555 nm region have been rotationally analyzed and give a bond length in the ground state of 0.2059 nm. A vibrational frequency ω_e ≈ 485 cm⁻¹ is estimated from dispersed fluorescence measurements.     

Rovibrational spectroscopy of the Fermi-interacting ν4 = 1 and ν3 = ν6 = 1 levels of DCF3

The high-resolution infrared spectrum of deuterated fluoroform (DCF₃) was studied in the 700 and 1200 cm⁻¹ regions, with the aim of assigning and analyzing the ν₄ CF₃ asymmetric stretching vibration. The Fermi-type anharmonic coupling between the ν₄ = 1 and ν₃ = ν₆ = 1 rovibrational levels, already mentioned in an early work of Ruoff et al. [Spectrochimica Acta Part A 31A (1975) 1099-1100], was studied here for the first time under high resolution. Assignments in the ν₃ + ν₆/ν₄ band system were confirmed and extended by the identification of the ν₃ + ν₆ − ν₆ and ν₄-ν₆ bands in the 700 cm⁻¹ region, the latter being enhanced near the Fermi crossings of the studied levels. Data from both the hot and difference bands were included in the analysis. The close separation of the studied vibrational levels of about 14.8 cm⁻¹ produces a large variety of resonance crossings which involve levels with . Besides the Fermi () and Coriolis () resonances, they were accounted for by inclusion of additional higher-order ( and ) interaction terms between the vibrational states. The least-squares fit of more that 16,000 vibration-rotation transitions provides a quantitative reproduction of data in all bands.     

The 2ν5 overtone bands of perchloryl fluoride

The high-resolution infrared spectra of the monoisotopic species F³⁵Cl¹⁶O₃, F³⁷Cl¹⁶O₃, F³⁵Cl¹⁸O₃ and F³⁷Cl¹⁸O₃ have been studied in the region of the 2ν₅ overtones, from 1100 to 1200 cm⁻¹. Both the parallel and the perpendicular components are clearly observed in the spectra, their origins differing by about 0.4 cm⁻¹. In each spectrum about 2000 transitions have been assigned, 35% of them belonging to . The parallel and perpendicular bands in each manifold have been analyzed separately since no evidence of perturbations has been observed. The rovibration parameters of the v₅ = 2, l₅ = 0 and v₅ = 2, l₅=?2 excited states have been obtained. For the four species combining the and band origins with those of the ν₅ fundamentals the harmonic wavenumbers, , and the x₅₅ and g₅₅ anharmonicity constants have also been derived.     

High-temperature UV absorption of methyl radicals behind shock waves

The absorption of ultraviolet narrow-line laser radiation by methyl radicals (CH₃) in the electronic system has been studied at high temperatures behind shock waves. Methyl radicals at high temperatures were generated by the shock heating of methyl precursors: azomethane, methyl iodide, and ethane. The spectral shape and intensity of the broadband absorption feature from 211.5 to 220 nm at high temperature (1565 K) has been measured. The absorption coefficient of CH₃ at 216.62 nm, the wavelength of peak absorption at high temperatures in the P+Q band, has been determined from 1200 to 2500 K. Additionally, the absorption coefficients of several interfering UV-absorbing combustion species (, and C₃H₆) have been determined at 216.62 nm.     

Atomic structure of thin dysprosium-silicide layers on Si(1 1 1)

We report on scanning tunneling microscopy results of thin dysprosium-silicide layers formed on Si(1 1 1). In the submonolayer regime, both a and a 5 × 2 superstructure were found. Based on images taken at different tunneling conditions, a structure model could be developed for the superstructure. For one monolayer, a 1 × 1 superstructure based on hexagonal DySi₂ was observed, while several monolayers thick films are characterized by a superstructure from Dy₃Si₅.     

Ultra-thin films and surface alloying of Pd on Cu(1 1 1) investigated by medium energy ion scattering

The structure of Pd films on Cu(1 1 1) and the alloying between the films and the substrate have been investigated by medium energy ion scattering (MEIS) using 100 keV H⁺ ions. Data are presented for the and alignments (nominal one- and three-layer alignments, respectively). It is found that beyond 1 ML the Pd grows in a twinned fcc structure, the incommensurate nature of which increases the visibility of the Cu(1 1 1) substrate to MEIS. Deposition of 0.2 ML of Pd produces a structure in which Pd mostly occupies the top two layers which have interlayer distances d₁₂ = 208 ± 4 pm and d₂₃ = 211 ± 4 pm. Some twinning is also present in this structure. Upon annealing 1.6 ML of Pd to 600 K for 1 min, the copper and palladium interdiffuse leaving around 0.4 ML of visible palladium. Energy plots show that there are several layers with an altered structure present over at least part of the surface. This may be due to large scale interdiffusion or alloy island formation. Incremental annealing to successively higher temperatures shows that the structural transformation begins around 500 K.