New line intensity measurements for C2H2 around 7.7 μm and HITRAN format line list for applications

Absolute intensities of 467 lines are measured in 9 bands of the 7.7 μm spectral region of the ¹²C₂H₂ molecule, with an average accuracy of 5%. For each band, the vibrational transition dipole moment squared and Herman-Wallis coefficients are obtained in order to model the rotational dependence of the transition dipole moment squared. These results are used to calculate a line list for atmospheric or astrophysical applications. Merged in the line list set up in a previous work for the 8 strongest bands around 7.7 μm [5], these new data give now a quasi-exhaustive view of the ¹²C₂H₂ spectrum in the involved spectral region.     

New CW-CRDS measurements and global modeling of CO2 absolute line intensities in the 1.6 μm region

Line intensities of ¹²C¹⁶O₂ transitions have been measured by CW-Cavity Ring Down Spectroscopy in four wavenumber intervals near 1.6 μm. Intensity values of 952 transitions ranging from 1.10 × 10⁻²⁸ to 4.94 × 10⁻²⁵ cm/molecule were retrieved with an average accuracy of 4%. These transitions belong to a total of 30 bands corresponding to the ΔP = 9 series of transitions. The achieved sensitivity (noise equivalent absorption α_min ∼ 3 × 10⁻¹⁰ cm⁻¹) allows lowering by more than two orders of magnitude the lower intensity values measured in the region. Comparison with the values included in the JPL database [R.A. Toth, L.R. Brown, C.E. Miller, V. Malathi Devi, D.C. Benner, J. Quant. Spectrosc. Radiat. Transf. 109 (2008) 906-921] shows residuals exceeding one order of magnitude for weak lines. The measured intensities together with a selection of experimental intensities available in the literature were used to extend and refine the set of effective dipole moment parameters for the ΔP = 9 series of transitions of the principal isotopologue of carbon dioxide. The refined parameters allow reproducing, within the experimental uncertainties, the whole set of intensity measurements which extends over nearly six orders of magnitude (1.10 × 10⁻²⁸-6.12 × 10⁻²³ cm/molecule). Combining the CW-CRDS line positions with the calculated line intensities, a line list has been generated for the whole 5851-7045 cm⁻¹ region and is provided as Supplementary Material. The obtained effective dipole moment parameters have also been used to generate the ΔP = 9 series of transitions included in the new version of the CDSD database. The comparison of the CDSD line intensities with the values provided by the HITRAN-2004 database shows discrepancies up to 80% for some of the bands while discrepancies up to three orders of magnitude are noted for the weakest bands included in the JPL database.     

6.2 W laser-diode end-pumped continuous-wave Nd:YALO3 laser at 1.34 μm

We report a compact and efficient LD end-pumped linearly polarized Nd:YAP laser operating at 1.34 μm. The laser system with different crystal lengths, output couplers and cavity types were compared. Based on optimizing of the pump system and laser cavity, 6.2 W laser radiation at 1341.4 nm with c-axis polarized was achieved, corresponding to an optical conversion efficiency of about 24.8% with respect to the incident pump power. The laser threshold was only about 1.3 W and the optical slope efficiency was up to 27.2%.     

Tunable diode laser measurement of pressure-induced shift coefficients of CO2 around 2.05 μm for Lidar application

Atmospheric carbon dioxide (CO₂) is one of the main contributors to the greenhouse effect. A global monitoring of CO₂ from space is foreseen as a key issue to quantify its sources and sinks at a regional scale and to better predict future levels of CO₂ and their effect on climate change. Differential Absorption Lidar (DiAL) is a promising and novel spectroscopic technique for remote sensing CO₂ spatial and temporal concentration distribution with a high level of accuracy. However, a precise knowledge of spectroscopic parameters of CO₂ molecular transitions and their dependence with temperature and pressure is required for reducing the uncertainty on DiAl measurements. Hence, to support remote sensing of carbon dioxide in the troposphere, we report on the accurate determination of air pressure-induced shift coefficients for eight absorption lines belonging to the R branch of (20⁰1)_III←(00⁰0)_I band of CO₂ at 2.05 μm. Purposely, a high-resolution tunable diode laser absorption spectrometer (TDLAS) coupled to a cryogenically cooled optical cell was implemented. From these measurements, we have further determined the temperature-dependencies of the air pressure-induced shift coefficients.     

Interaction of H2S with α-Fe2O3(0 0 0 1) surface

The atomic-scale structural changes in an α-Fe₂O₃ (hematite) (0 0 0 1) surface induced by sulfidation and subsequent oxidation processes were studied by X-ray photoemission spectroscopy, LEED, and X-ray standing wave (XSW) measurements. Annealing the α-Fe₂O₃(0 0 0 1) with a H₂S partial pressure of 1 × 10⁻⁷ Torr produced iron sulfides on the surface as the sulfur atoms reacted with the substrate Fe ions. The oxidation state of the substrate Fe changed from 3+ to 2+ as a result of the sulfidation. The XSW measured distance of the sulfur atomic-layer from the unrelaxed substrate oxygen layer was 3.16 Å. The sulfide phase consisted of three surface domains identified by LEED. Formation of the two-dimensional FeS₂ phase with structural parameters consistent with an outermost layer of (1 1 1) pyrite has been proposed. Atomic oxygen exposure oxidized the surface sulfide to a sulfate () and regenerated the α-Fe₂O₃(0 0 0 1) substrate, which was indicated by a (1 × 1) LEED pattern and the re-oxidization of Fe to 3+.     

Line parameters of H2O around 0.8 μm studied by tuneable diode laser spectroscopy

The absorption spectrum of H₂O has been extensively studied over the past decades in the near-infrared and visible regions, but there remain significant discrepancies in the 10,000-12,500 cm⁻¹ range even for the most intense lines. We have studied 24 lines of H₂O using an external-cavity diode laser emitting in the 810-830 nm range, in order to measure absolute line intensities as well as air- and self-broadening coefficients. Comparisons were made with values obtained from the HITRAN database and also with other parameters from recent experiments or predicted calculations. It is suggested that neglecting the effects of H₂O collisional narrowing in radiative transfer calculations of the Earth's atmosphere may have a small but significant impact on the radiative budget of the Earth.     

The overtone spectrum of C2D2 and C2H2 by ICLAS-VECSEL near 1 μm

The intracavity laser absorption spectra (ICLAS) of dideuteroacetylene, C₂D₂, and acetylene, C₂H₂, have been recorded between 1.03 and 0.99 μm with a vertical external cavity surface emitting laser (VECSEL) leading to the observation of seven and six bands, for C₂D₂ and C₂H₂ respectively, most of them newly reported. The strong ν₁+3ν₃ band of C₂D₂ at is found accompanied by the two Π-Π hot bands with v₄=1 and v₅=1 lower state and by the ν₂+3ν₃+2ν₄ band near . This last band results from an intensity transfer from the ν₁+3ν₃ band induced by the 1/244 anharmonic interaction. The ν₁+3ν₃ band of , present in natural abundance in the sample, could also be detected at in full agreement with local mode model predictions. The different bands of both C₂H₂ and C₂D₂ were found mostly unperturbed and the spectroscopic parameters retrieved from the rovibrational analyses agree satisfactorily with the predictions of the respective effective Hamiltonian models.     

Non-universal dielectric relaxation in SrFeO3 − δ

SrFeO_3 − δ compound is prepared by the thermal decomposition method followed by ball milling. Analysis of Mössbauer spectrum and X-ray diffraction study proves the presence of multi-phase nature, i.e., Sr₈Fe₈O₂₃ and Sr₄Fe₄O₁₁ phases at room temperature. Furthermore, the Mössbauer spectrum at room temperature evidenced the presence of major Fe^3.5+ which is the resultant of equal contributions of Fe⁴⁺ and Fe³⁺. The Nyquist plot at all measured temperatures (80–230 K) suggests that the dielectric response is well associated with single relaxation time (exponential parameter, n∼1$n\sim 1$) i.e., the Debye-type. Modulus analysis exhibits the non-universal dielectric behaviour (stretched exponential parameter, β>1$\beta >1$) below 230 K and the Debye-type responds (β∼1$\beta \sim 1$) at and above 230 K. The Debye-type behaviour exhibited by SrFeO_2.81 at around room temperature in its defect state offers a new opening for this material for multifunctional applications.     

Infrared absorption cross sections for ethane (C2H6) in the 3 μm region

Infrared absorption cross sections for ethane have been measured in the 3 μm spectral region from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125/HR). Results are presented for pure ethane gas from spectra recorded at 0.004 cm⁻¹ resolution and for mixtures with dry synthetic air from spectra obtained at 0.015 cm⁻¹ resolution (calculated as 0.9/MOPD using the Bruker definition of resolution), at a number of temperatures and pressures appropriate for atmospheric conditions. Intensities were calibrated using three ethane spectra (recorded at 278, 293, and 323 K) taken from the Pacific Northwest National Laboratory (PNNL) IR database.     

Highly thermal stable transparent conducting SnO2:Sb epitaxial films prepared on α-Al2O3 (0 0 0 1) by MOCVD

Antimony-doped tin oxide (SnO₂:Sb) single crystalline films have been prepared on α-Al₂O₃ (0 0 0 1) substrates by metal organic chemical vapor deposition (MOCVD). The antimony doping was varied from 2% to 7% (atomic ratio). Post-deposition annealing of the SnO₂:Sb films was carried out at 700-1100 °C for 30 min in atmosphere ambient. The effect of annealing on the structural, electrical and optical properties of the films was investigated in detail. All the SnO₂:Sb films had good thermal stability under 900 °C, and the 5% Sb-doped SnO₂ film exhibited the best opto-electrical properties. Annealed above 900 °C, the 7% Sb-doped SnO₂ film still kept high thermal stability and showed good electrical and optical properties even at 1100 °C.     

Investigation of 1.06 μm laser induced plasma in air using optical interferometry

The laser produced plasma in air by Q-switch Nd:YAG pulses with 50 mJ and 7 ns was analyzed using Mach-Zehnder interferometer. The interferograms were taken at various delay times after single pulses induced gas breakdown. The 3D electron density distribution at early times of the plasma is investigated. To determine the 3D electron density distribution of the plasma, the FFT analysis is applied to extract the phase of the reconstructed interferograms and the numerical inverse Abel transformation is used to calculate the refractive index. The results provide an understanding of the electron density temporal and spatial evolution of laser induced plasma in air from 18 ns and up to 100 ns of plasma lifetime.     

Structural and photoluminescence properties of SnO2:Ga films deposited on α-Al2O3 (0 0 0 1) by MOCVD

Gallium-doped tin oxide (SnO₂:Ga) films have been prepared on α-Al₂O₃ (0 0 0 1) substrates at 500 °C by the pulse mode metalorganic chemical vapor deposition (MOCVD) method. The relative amount of Ga (Ga/(Ga+Sn) atomic ratio) varied from 3% to 15%. Post-deposition annealing of the films was carried out at different temperatures for 1.5 h in ambient atmosphere . The structural, electrical, optical and photoluminescence (PL) properties of the films have been investigated as a function of annealing temperature. All the films have the rutile structure of pure SnO₂ with a strong (2 0 0) preferred orientation. A single ultraviolet (UV) PL peak near 337.83 nm was observed at room temperature for the 3% Ga-doped as-grown film and near 336 nm for the 15%-doped film, which can be ascribed to electron transition from the oxygen vacancy and interstitial Ga³⁺ donor levels to the acceptor level formed by the substitution of Ga³⁺ for the Sn site. After annealing, the luminescence spectra have changed a little bit, which is being discussed in detail.     

Continuous-tunable 4.144-4.851 μm twin-MgO:PPLN cascaded optical parametric generator pumped by a 1.342 μm Nd:GdVO4 laser

An all-solid-state mid-infrared optical parametric generator with wide tunability by using multi-grating periodically poled 5 mol.-% MgO-doped lithium niobate (MgO:PPLN) is reported. The pump source is a diode-pumped Q-switched Nd:GdVO₄ laser operated at 1.342 μm with pulse width of 150 ns and repetition rate of 50 kHz. To extend the interaction length, two identical multi-grating MgO:PPLN crystals have been cascaded in the OPG system. When the incident pump average power is 10 W, the obtained maximum idler output power is 340 mW at 4.144 μm. Compared with only using one multi-grating MgO:PPLN crystal, the obtained idler output power increases by 20.1%. 4.144-4.851 μm continuous-tunable idler output is obtained with six grating periods from 29 to 31.5 μm and temperature from 40 to 200 °C. To our knowledge, this is the first time to use 1.342 μm laser as the pump source of OPG.     

Surface studies of 2,4-pentanedione on γ-Al2O3/NiAl (1 0 0) and NiAl (1 0 0)

The chemical compound 2,4-pentanedione (Hacac) has been shown to etch the oxidized metal surfaces metals such as copper and nickel, but not their unoxidized surfaces. Here it is shown that on the γ-Al₂O₃/NiAl (1 0 0) surface (oxidized NiAl (1 0 0)) etching of aluminum occurs at 170 K and 750 K. Reflection-absorption infrared spectroscopy (RAIRS) is used to show that Hacac binds to both the clean, metallic and oxidized surfaces, but decomposition and combustion products dominate on the metallic surface and no etching occurs. The binding process that involves a deprotonation reaction of the enol species was identified by redshift in the carbonyl peaks and the appearance of an Al-H peak observed in the IR spectrum. The implication of these results is that there is both an unusual low temperature and high temperature etching of the alumina by bound acac.     

HCOOH high-resolution spectroscopy in the 9.18 μm region

We report on highly accurate absolute frequency measurement against a femtosecond frequency comb of six saturated absorption lines of formic acid (HCOOH) with an accuracy of 1 kHz. We also report the frequency measurement of 17 other lines with an accuracy of 2 kHz. Those lines are in quasi coincidence with the 9R(36) to 9R(42) CO₂ laser emission lines and are probed either by a CO₂ or a widely tunable quantum cascade laser phase locked to a master CO₂ laser. The stability of HCOOH stabilized lasers is characterized by a fractional Allan deviation of 3.1 × 10⁻¹² τ^−1/2. They give suitable frequency references for Doppler-free two-photon spectroscopy.     

Oxidation mechanism and ferryl domain formation on the α-Fe2O3 (0 0 0 1) surface

Recent experimental evidence calls for a reinterpretation of the oxidized structure in chemically distinct domains of the hematite (0 0 0 1) surface as the ferryl (FeO) termination rather than the bulk terminated O₃-Fe-Fe-R structure. Although this interpretation is consistent with experimental data and ab initio thermodynamics calculations, it raises serious questions about how molecular oxygen can be dissociated on a surface where reactive iron centers are slightly more than 5 Å apart. Here, we propose a novel cooperative bimolecular mechanism that provides a reasonable pathway for the formation of the unusual ferryl surface termination and should be readily reversible, which is important for understanding the function of hematite surfaces as an oxidation catalyst.     

Graphene-based passively Q-switched 2 μm thulium-doped fiber laser

We demonstrated stable pulses generation at 2 μm in a passively Q-switched thulium-doped fiber laser using a few layer graphene thin film. The maximum output power was 4.5 mW and the single pulse energy was 85 nJ at 53 kHz repetition rate, and the pulse width was about 1.4 μs. The pulse width and the repetition rate of the Q-switched fiber laser can be changed along with the pump power. To the best of our knowledge, this is the first report of graphene saturable absorber for passively Q-switched 2 μm fiber lasers.     

Experimental low energy values of CH4 transitions near 1.33 μm by absorption spectroscopy at 81 K

The high resolution absorption spectrum of methane has been recorded at liquid nitrogen temperature by direct absorption spectroscopy between 1.36 and 1.30 μm (7351-7655 cm⁻¹) using a cryogenic cell and a series of distributed feed back (DFB) diode lasers. The investigated spectral range corresponds to the high energy part of the icosad dominated by the ν₂+2ν₃ band near 7510 cm⁻¹. The positions and strengths at 81 K of 3473 transitions were obtained from the spectrum analysis. The minimum value of the measured line intensities (at 81 K) is on the order of 10⁻²⁶ cm/molecule, i.e. significantly lower than the intensity cut off of the HITRAN database in the region (4×10⁻²⁵ cm/molecule at 296 K). From the variation of the line strength between 81 and 296 K, the low energy values of 1273 transitions could be determined. They represent 69% and 81% of the absorbance in the region at 296 and 81 K, respectively. The obtained results are discussed in relation with the few rovibrational assignments previously reported in the region.     

Surface and redox chemistry of Sm0.95Ce0.05Fe1 − xNixO3 − δ perovskites

A new series of perovskite materials with formula Sm_0.95Ce_0.05Fe_1 − xNi_xO_3 − δ (0 ≤ x ≤ 0.10) has been prepared by sol-gel combustion via a citrate precursor route. X-ray diffraction data showed that materials prepared by this method had a single orthorhombic phase belonging to the Pnma (62) space group. The study of powders sintered in air and in reducing atmospheres reveals that these materials do not show phase separation in air (up to 1350 °C) nor under 5% v/v H₂/N₂ (up to 700 °C), but a phase separation of Sm₂O₃ does occur at and above 800 °C under 5% v/v H₂/N₂ without deterioration of the perovskite phase. The surfaces of all the powders (fresh, in-situ reduced and ex-situ reduced) were Sm rich, and multiple oxidation states for Fe were observed. XP analysis of in-situ reduced samples (800 °C and above) shows that metallic Fe forms in all nickel doped materials except x = 0.07. The surface oxygen vacancies and percentages of lattice and adsorbed oxygen for this series of Ni doped materials were determined and the oxygen recapturing ability is explained in terms of the multiple oxidation states of Fe.     

Antiferroelectric phase transition in pyrochlore-like (Dy1− xCax)2Ti2O7 − δ (x = 0, 0.1) high temperature conductors

Low-temperature ordering transitions in polycrystalline high temperature conductors (Dy_1 − xCa_x)₂Ti₂O_7 − δ (x = 0, 0.1) prepared using co-precipitation, mechanical activation and solid-state reactions at 1400 or 1600 °C have been studied by impedance spectroscopy at low frequencies and thermal mechanical analysis (TMA). The dielectric permittivity and loss tangent of the ceramics obtained have been measured as a function of temperature at low frequencies (0.5−500 Hz). The results provide evidence for the relaxation of point defects, most likely oxygen vacancies, at 500−600 °C and an antiferroelectric low-temperature phase transition of the second order, associated with re-arrangement process in the oxygen sublattice of pyrochlore structure. The temperature of the antiferroelectric transition is 700 to 800 °C, depending on the synthesis procedure and ceramic composition. Calcium doping of Dy₂Ti₂O₇ leads to the formation of additional oxygen vacancies and, in the case of the samples prepared via co-precipitation, increases the peaks in permittivity due to the relaxation process and ordering transition by three or six times, respectively.