Measurements of the infrared absorption cross-sections of HCFC-141b (CH3CFCl2)

Detection of atmospheric trace gases by optical remote sensing techniques relies on the availability of molecular absorption spectra over a range of relevant temperatures. Absorption cross-sections of a pure vapour of the hydrochlorofluorocarbon HCFC-141b are reported at a resolution of 0.02 cm^?1 for a range of temperatures between 223 and 283 K and a spectral range of 570–3100 cm^?1. The integrated intensities of the nine main harmonic bands compare well with the data available from previous experimental studies and with theoretical calculations by ab initio and density functional theories.     

UV Fourier transform absorption cross sections of benzene,toluene, meta-, ortho-, and para-xylene

New measurements of the absorption cross sections of gaseous benzene, toluene, meta-, ortho-, and para-xylene have been performed with a Fourier transform spectrometer Bruker IFS120 M at the resolution of 1 cm^?1 over the 30 000–42 000 cm^?1 spectral range. The recordings were carried out under different pressure and temperature conditions with pure samples. The effect of the temperature on the absorption cross sections is investigated. Comparison with the literature shows large differences, largely attributed to the experimental difficulties encountered during these previous measurements and to a resolution effect. To our knowledge, it is the first time that such a dataset of UV absorption cross sections with temperature dependence is reported in the literature. Such data should be useful for upcoming remote sensing applications, such as atmospheric studies both on Earth and on other planets.     

Infrared spectra of high coverage CO adsorption structures on Pt(111)

The adsorption of carbon monoxide on Pt(111) was studied using polarization modulation infrared reflection absorption spectroscopy (PM-IRAS) and sum frequency generation (SFG) spectroscopy. Two CO on-top signals at 2110 cm^? 1 and 2097 cm^? 1 have been detected under continuous CO exposure in a pressure range from 10^? 7 to 100 mbar and at temperatures between 200 K and 300 K. The formation of the higher wavenumber signal is found to be kinetically limited below 200 K and by the presence of a stable c(4 × 2) adlayer in UHV. On the basis of the results presented in this study and previous experimental findings the two on-top signals are related to different CO compression layers on Pt(111) with θ > 0.5, hexagonal Moiré lattices and rectangular coincident site lattices.     

Photo-absorption studies on carbonyl sulphide in 30,000–91,000 cm−1 region using synchrotron radiation

Photo-absorption spectrum of carbonyl sulphide (OCS) is recorded in 30,000–91,000 cm^?1 (3300–1050 Å) region at an average resolution of 1.2 Å using Photo-physics beamline on the 450 MeV Indus-1 synchrotron radiation source at RRCAT Indore, India. Owing to significant absorption cross section dependence, spectra of OCS are recorded at various pressures (0.001–5 mbar) to optimize the S/N ratio for band systems appearing at different energy regions. The spectral region below 70,000 cm^?1 has contributions from dissociation mechanism of the ground state of OCS and three valence band systems arising from promotion of a 3π electron to 4π and 10σ orbital. Improved S/N ratio helped in unambiguous assignment of the valence band progressions at 42,000–48,000 cm^?1, 53,000–62,000 cm^?1 and 63,500–70,000 cm^?1 regions to the ¹Δ←X¹Σ⁺ transition, the relatively intense and sharp bands of ¹Π←X¹Σ⁺ transition and intense but broad bands of ¹Σ⁺←X¹Σ⁺ transition, respectively, and obtain the vibrational frequencies. Above 70,000 cm^?1 Rydberg series arising from s, p, d and f orbitals converging to the ionic ground state X²Π of OCS⁺ (90,121 cm^?1) are identified. Long progression in the first few members of the Rydberg series is suggestive of mixed valence character. Quantum defects are evaluated and used to discuss the nature of the molecular orbital. The present study provides a unifying picture of the VUV photo-absorption spectrum of OCS up to its first ionization limit.     

The near infrared cavity-enhanced absorption spectrum of methyl cyanide

The absorption spectrum of methyl cyanide (CH₃CN) has been measured in the near IR between 6000 and 8000 cm^?1 with a resolution of 0.12 cm^?1 using Fourier transform incoherent broadband cavity-enhanced absorption spectroscopy. The spectrum contains several weakly perturbed spectral regions; potential vibrational combination bands contributing to the spectrum are outlined. Line positions and cross-sections of CH₃CN between 6814 and 7067 cm^?1 have been measured at high-resolution of 0.001 cm^?1 using diode laser based off-axis cavity-enhanced absorption spectroscopy. A total of 4630 new absorption lines of CH₃CN are identified in this region. A value for the self-broadening coefficient has determined to be (3.3±0.2)×10^?3 cm^?1 mbar^?1 for one isolated line at 7034.171 cm^?1. Several line series have been identified in these regions and an autocorrelation analysis performed with a view to aiding future assignments of the rotational-vibrational transitions.     

Water-vapor continuum absorption in the 800–1250 cm−1 spectral region at temperatures from 311 to 363 K

About 200 pure water-vapor spectra covering the region from 800 to 3500 cm^?1 were recorded with resolution of 0.1 cm^?1 at temperatures 311, 318, 325, 339, 352, and 363 K using a 2 m base White cell coupled to the BOMEM DA3.002 FTIR spectrometer. The water-vapor pressure varied from 28 to 151 mbar (21–113 Torr). Under these conditions, the continuum absorbance is quite measurable with the available path lengths up to 116 m. A program was developed for spectral processing that calculates, fits, and removes ro-vibrational structure from the spectrum. The spectra obtained were used to retrieve averaged and smoothed binary absorption coefficients over the region from 800 to 1250 cm^?1. Our continuum data extrapolated to room temperature are in reasonable agreement with the MT_CKD continuum model. But at higher temperatures the MT_CKD model provides very low values, which are up to 50% less than those experimentally measured.     

Unexpected temperature rise in end-pumped Nd3+:YAG composite slab laser

Unexpected temperature rise is observed in end-pumped YAG–Nd³⁺:YAG–YAG slab laser experimentally. The measured optical absorption spectrum of undoped YAG in 780–830 nm indicates an absorption coefficient of 0.015 cm^?1 at 808 nm. The influence of the weak absorption on temperature distribution in end-pumped composite slabs is analyzed numerically and a good agreement with infrared measurement is achieved. The results of finite element analysis show that longer heat sinks and wider slabs bring lower temperature.     

ICLAS of water in the 770 nm transparency window (12 746–13 558 cm−1). Comparison with current experimental and calculated databases

The absorption spectrum of water vapor has been investigated by intracavity laser spectroscopy (ICLAS) in the 12 746–13 558 cm^?1 spectral region corresponding to an interesting transparency window of the atmosphere, partly obscured by the A band of molecular oxygen.The achieved sensitivity—in the order of α_min～10^?9 cm^?1—has allowed one to measure 1062 water lines with intensities ranging from 1.6×10^?28 to 2.35×10^?24 cm/molecule at 296 K. A total of 169 new and improved energy levels belonging to 21 vibrational states could be determined from 374 newly measured transitions. The retrieved experimental line list is compared with the spectra calculated by Schwenke and Partridge, and Barber and Tennyson. Comparison with the available experimental databases shows that the obtained results represent a significant improvement of the knowledge of the water absorption in the considered region, in particular in the region of the oxygen A band.     

Refinements of the WKMC empirical line lists (5852–7919 cm−1) for methane between 80 K and 296 K

During the last 4 years, empirical line lists for methane at room temperature and at 80 K were constructed from spectra recorded by (i) differential absorption spectroscopy (DAS) in the high energy part of the tetradecad (5852?6195 cm^?1) and in the icosad (6717–7589 cm^?1) and (ii) high sensitivity CW-Cavity Ring Down Spectroscopy (CRDS) in the 1.58 μm and 1.28 μm transparency windows (6165–6750 cm^?1 and 7541–7919 cm^?1, respectively). We have recently constructed the global line lists for methane in “natural” isotopic abundance, covering the spectral region from 5854 to 7919 cm^?1 (Campargue A, Wang L, Kassi S, Mondelain D, Bézard B, Lellouch E, et al., An empirical line list for methane in the 1.26–1.71 μm region for planetary investigations (T=80–300 K). Application to Titan, Icarus 219 (2012) 110–128). These WKMC (Wang, Kassi, Mondelain, Campargue) empirical lists include about 43,000 and 46,420 lines at 80±3 K and 296±3 K, respectively. The “two temperature method” provided lower state energy values, E_emp, for about 24,000 transitions allowing us to account satisfactorily for the temperature dependence of the methane absorption over the considered region. The obtained lists have been already successfully applied in a large range of temperature conditions existing on Titan, Uranus, Pluto, Saturn and Jupiter.In the present contribution, we provide some improvements to our lists by using literature data to extend the set of lower state energy values and by correcting the distortion of the high E_emp values (J>10) due to the temperature gradient existing in the cryogenic cell used for the recordings. The proposed refinements are found to have an overall limited impact but they may be significant in some spectral intervals below 6500 cm^?1.The new version of our lists at 80 K and 296 K is provided as Supplementary Material: the WKMC@80K+ and WKMC@296K lists are adapted for planetary and atmospheric applications, respectively. The WKMC@80K+ list is made applicable over a wider range of temperatures and shows satisfactory extrapolation capabilities up to room temperature. It was obtained by transferring to the 80 K list the 27,580 single lines present only in the 296 K list, with corresponding lower state energy values chosen to make them below the detectivity limit at 80 K.In the discussion, the different line lists and databases available for methane in the near infrared are compared and some suggestions are given.     

Critical evaluation of measured rotation–vibration transitions and an experimental dataset of energy levels of HD18O

All available transitions from microwave to visible region (0.2–12 105 cm^?1) of the HD¹⁸O molecule were collected and tested using the RITZ computer code. Literature data were completed by transitions assigned to HD¹⁸O in long path Fourier transform absorption spectra of the H₂O, HDO and D₂O gas mixtures with natural abundance of oxygen-18. In addition about 40 unassigned lines between 4200 and 6600 cm^?1 of our previous water study associated with the HD¹⁸O molecule have been found and assigned. The new long path absorption spectra of the HDO and D₂O mixtures allow us to observe about 1000 transitions of HD¹⁸O in the 6125–10 720 cm^?1 spectral region. These data have been critically analyzed and used to obtain the most complete and precise set of the experimental energy levels of this molecule.     

Infrared absorption cross sections for methanol

Infrared absorption cross sections for methanol, CH₃OH, have been determined near 3.4 and 10 μm from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125HR) and a multipass cell with a maximum optical path length of 19.3 m. Methanol/dry synthetic air mixtures were prepared and spectra were recorded at 0.015 cm^?1 resolution (calculated as 0.9/MOPD) at a number of temperatures and pressures (50–760 Torr and 204–296 K) appropriate for atmospheric conditions. Intensities were calibrated using composite methanol spectra taken from the Pacific Northwest National Laboratory (PNNL) IR database. The new measurements in the 10 μm region indicate problems with the existing methanol spectroscopic line parameters in the HITRAN database, which will impact the accuracy of satellite retrievals.     

Nonlinear optical properties of erbium doped zinc oxide (EZO) thin films

Undoped and Erbium (Er) doped zinc oxide (EZO) thin films were deposited on glass substrate by sol–gel method using spin coating technique with different doping concentration. EZO films were characterized using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), UV–VIS-NIR transmission and single beam z scan method under illumination of frequency doubled Nd:YAG laser. The deposited films were found to be well crystallized with hexagonal wurtzite structure having a preferential growth orientation along the ZnO (002) plane. A blue-shift was observed in the band gap of EZO films with increasing Er concentration. All the films exhibited a negative value of nonlinear refractive index (n₂) at 532 nm which is attributed to the two photon absorption and weak free carrier absorption. Third order nonlinear optical susceptibility, χ⁽³⁾ values of EZO films were observed in the remarkable range of 10^? 6 esu. EZO (0.4 at.%) sample was found to be the best optical limiter with limiting threshold of 1.95 KJ/cm².     

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.     

Structural investigation of Te-based chalcogenide glasses using Raman spectroscopy

Structural changes of metals (Zn, Sb, In, Ga) and metal halides (AgI, ZnI₂, CdI₂, PbI₂, BiI₃) modified GeTe₄ glasses were investigated with the aid of Raman spectroscopy. The Raman spectra of these glasses in the frequency region between 100 cm^?1 and 300 cm^?1 display four main bands at about 124, 140, 159 and 275 cm^?1 which are contributed by Ge–Te, Te–Te, Te–Te and Ge–Ge vibration modes. The intensity of 159 cm^?1 and 275 cm^?1 bands vary with the addition of different glass modifiers. While the relative intensity of the 124 cm^?1 and 140 cm^?1 bands are insensitive to composition changes. Glass modifiers like Zn, In and Sb act as glass network unstabilizer which will disorganize the glass network by opening up the chain structures of Ge–Te and Te–Te. In the case of Ga and metal halides, Ga can open up Ge–(Te–Te)_4/2 tetrahedra and form Ga–(Te–Te)_3/2 triangle. Iodine can form covalent bonds with tellurium and decrease the tendency of microcrystal formation. Thus both Ga and iodine ultimately act as glass network stabilizer.     

Extended line positions,intensities, empirical lower state energies and quantum assignments of NH3 from 6300 to 7000 cm−1

Nearly 4800 features of ammonia between 6300 and 7000 cm^?1 with intensities ≥4×10^?24 cm^?1/(molecule·cm^?2) at 296 K were measured using 16 pure NH₃ spectra recorded at various temperatures (296–185 K) with the McMath–Pierce Fourier Transform Spectrometer at Kitt Peak National Observatory, AZ. The line positions and intensities were retrieved by fitting individual spectra based on a Voigt line shape profile and then averaging the values to form the experimental linelist. The integrated intensity of the region was 4.68×10^?19 cm^?1/(molecule·cm^?2) at 296 K. Empirical lower state energies were also estimated for 3567 absorption line features using line intensities retrieved from 10 spectra recorded at gas temperature between 185 and 233 K. Finally, using Ground State Combination Differences (GSCDs) and the empirical lower state energy estimates, the quantum assignments were determined for 1096 transitions in the room temperature linelist, along with empirical upper state energies for 434 levels. The assignments correspond to seven vibrational states, as confirmed from recent ab initio calculations. The resulting composite database of ¹⁴NH₃ line parameters will provide experimental constraints to ab initio calculations and support remote sensing of gaseous bodies including the atmospheres of Earth, (exo)planets, brown dwarfs, and other astrophysical environments.     

High resolution emission spectroscopy of the E2Π–X2Σ+ transition of SrH and SrD

Emission spectra of SrH and SrD have been studied at high resolution using a Fourier transform spectrometer. The molecules have been produced in a high temperature furnace from the reaction of strontium metal vapor with H₂/D₂ in the presence of a slow flow of Ar gas. The spectra observed in the 18 000–19 500 cm^?1 region consist of the 0–0 and 1–1 bands of the E²Π–X²Σ⁺ transition of the two isotopologues. A rotational analysis of these bands has been obtained by combining the present measurements with previously available pure rotation and vibration–rotation measurements for the ground state, and improved spectroscopic constants have been obtained for the E²Π state. The present analysis provides spectroscopic constants for the E²Π state as ΔG(½) = 1166.1011(15) cm^?1, B_e = 3.805503(32) cm^?1, α_e = 0.098880(47) cm^?1, r_e = 2.1083727(89) Å for SrH, and ΔG(½) = 839.1283(23) cm^?1, B_e = 1.918564(15) cm^?1, α_e = 0.034719(23) cm^?1, r_e = 2.1121943(83) Å for SrD.     

Validation of HNO3 spectroscopic parameters using atmospheric absorption and emission measurements

The improved database of HNO₃ spectroscopic parameters in the 600–950 cm^?1 spectral region presented in [Gomez L, Tran H, Perrin A, Gamache RR, Laraia A, Orphal J, et al. Some improvements of the HNO₃ spectroscopic parameters in the spectral region from 600 to 950 cm^?1. JQSRT 2008, in press] is tested by comparisons between calculations and atmospheric remotely sensed absorption and emission spectra. The line parameters in the 11.3 μm region are validated using ground-based Fourier transform solar absorption measurements, whereas those in the 13.1 μm region are successfully tested using balloon-borne atmospheric emission spectra. In both regions, the quality of the line parameters and the consistency between band intensities is confirmed through comparisons with emission spectra collected by the satellite-borne MIPAS instrument.     

Mid- and long-wave infrared absorption cross sections for acetonitrile

Infrared absorption cross sections for acetonitrile (methyl cyanide; CH₃CN) have been determined in the 880–1700 cm^?1 spectral region from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125 HR) and a multipass cell with a maximum optical pathlength of 19.3 m. Spectra of acetonitrile/dry synthetic air mixtures were recorded at 0.015 cm^?1 resolution (calculated as the Bruker instrument resolution of 0.9/MOPD) at a number of temperatures between 203 and 297 K and pressures appropriate for atmospheric conditions. Intensities were calibrated using three composite acetonitrile spectra recorded at the Pacific Northwest National Laboratory. These absorption cross sections will provide an accurate basis for upper tropospheric/lower stratospheric retrievals of acetonitrile in the mid-infrared spectral region from ACE satellite data.     

Laser spectroscopic study of ozone in the 100←000 band for the SWIFT instrument

A complete spectroscopic study of 15 strong ozone lines in the 1132.5–1134.5 cm^?1 spectral range has been undertaken in the framework of the development of the stratospheric wind interferometer for transport studies (SWIFT), led by the Canadian Space Agency. Measurements have been performed with an interferometrically stabilized tunable diode laser spectrometer. Absolute line positions and intensities have been determined with high accuracy (4×10^?5 cm^?1 and 1–2% respectively). Self- and air-broadening coefficients at 296 K have been obtained with an accuracy of 1%. The air-shifting coefficient and its temperature dependence have also been measured for unblended lines together with the temperature dependence of the air-broadening. Line intensities have been calibrated by simultaneously performed UV absorption measurements at 253.7 nm. Our IR/UV comparison supports a previously reported inconsistency between recommended IR intensities (HITRAN08) and UV absorption cross-sections and indicates that current IR intensities are too small by ～3%.     

Fourier transform measurements of SO2 absorption cross sections:: I. Temperature dependence in the 24 000–29 000 cm−1 (345–420 nm) region

Absorption cross sections of SO₂ have been obtained in the 24 000–29 000 cm^?1 spectral range (345–420 nm) with a Fourier transform spectrometer at a resolution of 2 cm^?1. Pure SO₂ samples were used and measurements were performed at room temperature (298 K) as well as at 318, 338 and 358 K. This is the first time that temperature effects in this spectral region are reported and investigated. This paper is the first of a series that will report on measurements of the absorption cross section of SO₂ in the UV/visible region at a higher than previously reported resolution and that will investigate temperature effects in support of tropospheric, stratospheric and astrophysical or planetary applications.