Analysis of the CRDS spectrum of 18O3 between 6950 and 7125 cm−1

The absorption spectrum of the ¹⁸O₃ isotopologue of ozone was recorded by CW-Cavity Ring Down Spectroscopy in the 6950–7125 cm^?1 region. The typical noise equivalent absorption of the recordings is α_min ≈1×10^?10 cm^?1. The spectrum is dominated by three very weak bands: 3ν₁+5ν₃ near 7009 cm^?1 and the ν₂+7ν₃ and 4ν₂+5ν₃ interacting bands near 7100 cm^?1. In total 260, 206 and 133 transitions were assigned for the 3ν₁+5ν₃, ν₂+7ν₃ and 4ν₂+5ν₃ bands, respectively. The line positions of the 3ν₁+5ν₃ band were modelled using an effective Hamiltonian (EH) model involving two dark states – (6 0 1) and (2 5 2) – in interaction with the (3 0 5) bright state. The EH model developed for the ν₂+7ν₃ and 4ν₂+5ν₃ bands involves only the (0 1 7) and (0 4 5) interacting bright states. Line positions could be reproduced with rms deviations on the order of 0.01 cm^?1 and the dipole transition moment parameters were determined for the three observed bands. The obtained set of parameters and the experimentally determined energy levels were used to generate a list of 984 transitions of the three bands which is provided as Supplementary Material.     

Topmost-surface-sensitive Si-2p photoelectron spectra of clean Si(1 0 0)-2 × 1 measured with photoelectron Auger coincidence spectroscopy

Topmost-surface-sensitive Si-2p photoelectron spectra of a clean Si(1 0 0)-2 × 1 surface have been measured using Si-2p photoelectron Si-L₂₃VV Auger coincidence spectroscopy (Si-2p–Si-L₂₃VV PEACS). The escape depth of the PEACS electrons is estimated to be ～1.2 Å. The results support the assignments of the Si up-atoms, the Si down-atoms, the Si 2nd-layer, and the Si bulk proposed in previous researches. The Si-2p component with a binding energy of ?0.23 eV relative to the bulk Si-2p_3/2 peak, is shown to originate mainly from the topmost surface. Site selectivity of PEACS is indicated to be achieved to some degree by carefully selecting the kinetic energy of the Auger electrons. Since PEACS can be applied to any surface, the present study opens a new approach to identify PES components.     

CRDS of water vapor at 0.1 Torr between 6886 and 7406 cm−1

The absorption spectrum of water vapor in “natural” isotopic abundance has been recorded by high sensitivity CW-Cavity Ring Down Spectroscopy (CW-CRDS) between 6885.79 and 7405.91 cm^?1. This strong absorbing region includes the first hexad of interacting vibrational bands which was previously studied by Fourier Transform Spectroscopy. The achieved sensitivity of the recordings varies from α_min～2×10^–11 to 2×10^?10 cm^?1 allowing us to use a sample pressure of 0.1 Torr, making pressure broadening of the line profile mostly negligible. Weak lines in the vicinity of much stronger lines could then be accurately measured. The weakest lines have intensity on the order of 5×10^–28 cm/molecule at 296 K. A set of 4471 lines were assigned to 4916 transitions of five water isotopologues (H₂ ¹⁶O, H₂ ¹⁸O, H₂ ¹⁷O, HD¹⁶O and HD¹⁸O). A small number of new energy levels was determined mostly for the H₂ ¹⁷O isotopologue. The previous investigations and existing databases are critically evaluated. In particular, a number of corrections and new assignments are proposed for the water list provided by the HITRAN database in the considered region. As a result, a complete list of 12,700 transitions for water in “natural” isotopic abundance is provided as Supplementary Material for the 6885–7408 cm^?1 region.     

Detection and analysis of four new bands in CRDS 16O3 spectra between 7300 and 7600 cm−1

The absorption spectrum of the ¹⁶O₃ isotopologue of ozone was recorded in the 7000–7920 cm^?1 region by using high sensitivity CW-Cavity Ring Down Spectroscopy (α_min ～ 10^?10 cm^?1). This report is devoted to the analysis of the 7300–7600 cm^?1 region dominated by four A-type bands: 6ν₁ + ν₃ centred around 7395 cm^?1, 3ν₁ + 5ν₂ + ν₃ and 2ν₁ + 4ν₂ + 3ν₃ lying in the 7450 cm^?1 region and 5ν₁ + 2ν₂ + ν₃ centred around 7579 cm^?1. 213 transitions of the 6ν₁ + ν₃ band were assigned and the corresponding line positions were modeled using an effective Hamiltonian including a Coriolis resonance interaction between the (601) upper state and a A-type dark state. The two very close 3ν₁ + 5ν₂ + ν₃ and 2ν₁ + 4ν₂ + 3ν₃ bands were analysed using a similar effective Hamiltonian scheme involving the anharmonic resonance coupling between the (351) and (243) states. For these two bands, 304 transitions were assigned. The modelling also includes a first Coriolis resonance interaction between the (351) bright state and the (530) dark state, and a second one between the (243) bright state and the (144) dark state. In the 7579 cm^?1 region, 205 transitions of the 5ν₁ + 2ν₂ + ν₃ band were assigned and modelled taking into account the Coriolis resonance interactions between the (521) upper state and the (700), (342) and (280) dark states.The dipole transition moment parameters of the four analysed bands were determined by a least-squares fit to the measured line intensities. For the studied band systems, the effective Hamiltonian and transition moment operator parameters were used to generate line lists provided as Supplementary Materials.     

Effective line strengths of trans-nitrous acid near 1275 cm−1 and cis-nitrous acid at 1660 cm−1

We determined the effective line strengths of the trans conformer of nitrous acid (HONO) near 1275 cm^?1 (R-branch of ν₃ mode, NOH bend) and of the cis conformer at 1660 cm^?1 (R-branch of ν₂ mode, NO stretch), both at a spectral resolution of 0.001 cm^?1 by tunable infrared laser differential absorption spectroscopy (TILDAS) utilizing continuous-wave quantum cascade (cw-QC) lasers. Absorbance of one conformer was measured while simultaneously quantifying the mixing ratio of total HONO by catalytic conversion to nitric oxide (NO) followed by calibrated absorption spectroscopy. Line strengths obtained here are consistent with previously reported band strengths for the trans conformer but are lower by a factor of approximately 2.4 for the cis conformer.     

LED-based Fourier-transform spectroscopy of H2 18O in the range 15000–15700 cm−1

The spectrum of H₂ ¹⁸O in the range 15000–15700 cm^?1 has been recorded for the first time on a Fourier-transform spectrometer using a high-brightness light-emitting diode as a radiation source. The measurements have been conducted at room temperature with a resolution of 0.05 cm^?1. A threshold sensitivity in absorption of 2 × 10^?7 cm^?1 has been achieved due to both the use of a light-emitting diode and optimization of the multipass cell with a base length of 60 cm, which ensured a 19.2-m length of the absorbing layer. A high signal-to-noise ratio (S/N = 2000–10000) made it possible to record about 670 water-vapor lines with intensities of 1.0 × 10^?26–2.2 × 10^–24 cm/mol at 296 K. The energies of 265 vibrational-rotational levels of the H₂ ¹⁸O molecule are determined and attributed to seven vibrational states, namely, (033), (113), (212), (231), (311), (330), and (410).     

Preparation,surface state and band structure studies of SrTi(1 − x)Fe(x)O(3 − δ) (x = 0–1) perovskite-type nano structure by X-ray and ultraviolet photoelectron spectroscopy

In this report, SrTi_(1 ? x)Fe_(x)O_(3 ? δ) photocatalyst powder was synthesized by a high temperature solid state reaction method. The morphology, crystalline structures of obtained samples, was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and transmission electron microscopy (TEM), respectively. The electronic properties and local structure of the perovskite STF_x (0 ≤ x ≤ 1) systems have been probed by extended X-ray absorption fine structure (EXAFS) spectroscopy. The effects of iron doping level x (x = 0–1) on the crystal structure and chemical state of the STF_x have been investigated by X-ray photoelectron spectroscopy and the valence band edges for electronic band gaps were obtained for STF_x by ultraviolet photoelectron spectroscopy (UPS). A single cubic perovskite phase of STF_x oxide was successfully obtained at 1200 °C for 24 h by the solid state reaction method. The XPS results showed that the iron present in the STF_x perovskite structure is composed of a mixture of Fe³⁺ and Fe⁴⁺ (SrTi_(1 ? x)[Fe³⁺, Fe⁴⁺]_(x)O_(3 ? δ)). When the content x of iron doping was increased, the amount of Fe³⁺ and Fe⁴⁺ increased significantly and the oxygen lattice decreased on the surface of STF_x oxide. The UPS data has confirmed that with more substitution of iron, the position of the valence band decreased.     

Absorption spectroscopy of ammonia between 6526 and 6538 cm−1

The spectral measurements of ammonia absorption lines from 6526 to 6538 cm^?1 have been performed at room temperature by using fiber-coupled distributed feedback (DFB) diode laser operating at 1.531 μm. As many as 152 lines of ammonia and its line intensities, self-broadening and air-broadening coefficients were obtained, which include many weak lines not previously reported. The 20 strongest lines were obtained using the traditional direct absorption spectroscopy technology with a 30 cm single-path cell and the other 132 lines were acquired using a compact system based on off-axis integrated-cavity output spectroscopy (OA-ICOS) with an effective optical path of 36.62 m.     

The high-resolution infrared spectrum of HBF2: The 201 band near 1164 cm−1

The type-B totally symmetric stretching fundamental ν₂ (near 1164 cm⁻¹) of difluoroborane has been recorded. Rotational and centrifugal distortion constants have been evaluated for the two isotopic species H¹⁰BF₂ and H¹¹BF₂, in both the ground and 2¹ levels. The spectrum has been found to be regular, with no perturbations and no new information on the position of the missing fundamental ν₆.     

The high-resolution infrared spectrum of HBF2: The 401 band near 926 cm−1

The type-C out-of-plane bending fundamental ν₄ (near 926 cm⁻¹) in the infrared spectrum of gaseous difluoroborane, HBF₂, has been recorded at high resolution. Rotational and centrifugal distortion constants have been obtained for the two isotopic species H¹⁰BF₂ and H¹¹BF₂ in both the ground and 4¹ levels. A small rotational perturbation in the 4¹ level of H¹¹BF₂ has allowed an estimate of the position of the ν₆ fundamental, which so far has not been observed directly.     

Infrared spectroscopy of 17O- and 18O-enriched carbon dioxide in the 1700–8300 cm−1 wavenumber region

The assignment of the high resolution Fourier transform spectra of carbon dioxide enriched in ¹⁷O and ¹⁸O which were recorded in LADIR (Paris, France) with the Bruker IFS 125-HR between 1800 and 9000 cm^?1 and in USTC (Hefei, China) with the Bruker IFS 120-HR between 1700 and 9000 cm^?1 was performed. In total 239 bands of 12 isotopologues: ¹⁶O¹²C¹⁶O, ¹⁶O¹²C¹⁸O, ¹⁶O¹³C¹⁶O, ¹⁶O¹³C¹⁸O, ¹⁸O¹²C¹⁸O, ¹⁸O¹³C¹⁸O, ¹⁶O¹²C¹⁷O, ¹⁷O¹²C¹⁷O, ¹⁷O¹²C¹⁸O, ¹⁶O¹³C¹⁷O, ¹⁷O¹³C¹⁷O and ¹⁷O¹³C¹⁸O were observed. Among them, 99 bands were observed for the first time. The majority of new observed bands belong to ¹⁷OCO isotopologues. The positions of 23,003 lines were determined with the experimental uncertainty on the level of 0.001 cm^?1. The spectroscopic constants were fitted to the observed line positions for all observed bands.     

Atomic and nanostructures of monolayer c(2 × 2)NiN on Cu(0 0 1)

Structures of monolayer nickel nitride (NiN) on Cu(0 0 1) surface are studied by X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). Formations of Ni–N chemical bonds and NiN monolayer at the surface are confirmed by XPS on the N-adsorbed Cu(0 0 1) surfaces after Ni deposition and subsequent annealing to 670 K. A c(2 × 2) structure is always observed in the LEED patterns, which is a quite contrast to the (2 × 2)p4g structure observed usually at the N-adsorbed Ni(0 0 1) surface. Atomic images by STM indicate the mixture of Ni–N and Cu–N structures at the surface. Density of the trenches on the N-saturated surface decreases and the grid pattern on partially N-covered surfaces becomes disordered with increasing the Ni coverage. These results are attributed to the decrease of the surface compressive stress at the N-adsorbed Cu surface by mixing Ni atoms.     

Fourier transform infrared spectrum of carbon disulphide in the 4ν2 + ν3 band region near 3100 cm−1

Fourier transform spectra have been recorded for carbon disulphide CS₂ in the region of the 4ν₂ + ν₃ band near 3100 cm^?1. The data analysis has determined new molecular constants. Bands were also observed for the isotopomer ¹²C³²S³⁴S.     

Effect of Fe doping on the room temperature ferromagnetism in chemically synthesized (In1−xFex)2O3 (0 ⩽ x ⩽ 0.07) magnetic semiconductors

Observation of room temperature ferromagnetism in Fe doped In₂O₃ samples (In_1−xFe_x)₂O₃ (0 ⩽ x ⩽ 0.07) prepared by co-precipitation technique is reported. Lattice parameter obtained from powder X software shows distinct shrinkage of the lattice constant indicating an actual incorporation of Fe ions into the In₂O₃ lattice. X-ray diffraction data measurements show that the entire sample exhibits single phase polycrystalline behavior. SEM micrographs showed the prepared powder was in the range 25–36 nm. SEM EDS mapping showed the presence of Fe and In ions in the Fe doped In₂O₃ sample. The highest remanence magnetization moment (6.624 × 10⁻⁴ emu/g) is reached in the sample with x = 0.03.     

Some improvements of the HNO3 spectroscopic parameters in the spectral region from 600 to 950 cm−1

In an earlier study [Flaud JM, Brizzi G, Carlotti M, Perrin A, Ridolfi M. MIPAS database: validation of HNO₃ line parameters using MIPAS satellite measurements. Atmos Chem Phys 2006;6:1–12] the HNO₃ line parameters in the HITRAN spectroscopic database have recently been revisited in the interval corresponding to the MIPAS spectral range. For the 11.3 μm region these updates involve the line positions for the {ν₅, 2ν₉} bands, and the intensities. However, comparisons between observed spectra recorded by MIPAS and the calculated ones in the 600–950 cm^?1 region still show significant disagreements. The goal of the present paper is to solve some of these problems. Based on the analysis of N₂-broadened HNO₃ laboratory spectra recorded with a Fourier transform instrument, a new HNO₃ database was generated, including the following improvements: (i) approximate parameters for the ν₅+ν₇?ν₇ and ν₅+ν₆?ν₆ hot bands have been added, and (ii) the intensities for the ν₆ and ν₈ bands have been updated. (iii) The air broadening and its temperature dependence, calculated using a semi-classical approach, have been added for each HNO₃ transition. (iv) Finally, line-mixing effects have been pointed out, particularly in the ν₅+ν₉?ν₉ Q branch, and an approach correctly modeling the resulting spectral shape is proposed.     

Atomic structure of the (3 × 2) Si–GaAs (0 0 1) reconstructed surface: A clue to δ doping mechanism derived from in situ grazing incidence X-ray diffraction data

In view of understanding silicon incorporation in the δ doping process of GaAs (0 0 1), Si atoms have been deposited, under UHV, on a α(2 × 4) arsenic terminated substrate. In the low coverage regime, a transition to a less As rich (3 × 2) reconstructed Si–GaAs (0 0 1) surface was observed whose atomic structure has been investigated by grazing incidence X-ray diffraction performed in situ. Silicon is found to occupy not only a Ga substitutional site, precursor of a donor dopant but also to form nuclei for neutral clusters, on a template made by the (3 × 2) GaAs (0 0 1) reconstructed surface observed by Martrou et al. [Phys. Rev. B 72 (2005) 241307®]. The maximum surface concentration of donor-like silicon is estimated at 1.04 × 10¹⁴ cm^?2 (1/6th monolayer).     

Fourier transform measurements of H218O and HD18O in the spectral range 1000–2300 cm−1

The spectra of water vapor enriched by ¹⁸O were recorded in the 1000–2300 cm^?1 spectral range, which corresponds to the spectral region studied by IASI instrument (Infrared Atmospheric Sounding Spectrometer) instrument. The spectra were recorded by a step by step Fourier Transform Spectrometer (FTS) at room temperature with absorption path lengths up to 36 m. Positions, intensities and self broadening coefficients of about 1800 lines of H₂¹⁸O and 900 of HD¹⁸O were analyzed and all the transitions were assigned. This paper focuses on lines intensities and comparisons with data from literature are presented. An average difference of 10% with HITRAN2008 database H₂¹⁸O line intensities is found with a maximum discrepancy of about 25% for the ν₁–ν₂ band.     

Strained c(4 × 2) CoO(1 0 0)-like monolayer on Pd(1 0 0): Experiment and theory

We report on an interface-stabilized strained c(4 × 2) phase formed by cobalt oxide on Pd(1 0 0). The structural details and electronic properties of this oxide monolayer are elucidated by combination of scanning tunneling microscopy data, high resolution electron energy loss spectroscopy measurements and density functional theory. The c(4 × 2) periodicity is shown to arise from a rhombic array of Co vacancies, which form in a pseudomorphic CoO(1 0 0) monolayer to partially compensate for the compressive strain associated with the large lattice mismatch (～9.5%) between cobalt monoxide and the substrate. Deviation from the perfect 1:1 stoichiometry thus appears to offer a common and stable mechanism for strain release in Pd(1 0 0) supported monolayers of transition metal rocksalt monoxides of the first transition series, as very similar metal-deficient c(4 × 2) structures have been previously found for nickel and manganese oxides on the same substrate.