Qualifying IMG tropical spectra for clear sky

The problem of cloud detection for the Interferometric Monitoring of Greenhouse Gases spectrometer has been addressed by considering a set of thresholding tests which takes full advantage of the high spectral resolution of the sensor. The methodology has been applied to a case study consisting of spectra recorded in the tropics on sea surface, although the scheme may be easily extended to other latitudes. The algorithm is very efficient because it uses only the observed spectrum and no on-line radiative transfer calculation is needed. Based on this cloud detection scheme a set of clear-sky tropical spectra have been identified to be used by the scientific community for further studies such as retrieval of atmospheric properties and high spectral resolution radiative transfer modeling.     

Effects of vertical grid discretization in infrared transmission modeling

The vertical spacing of a discretization used to model transmission in the mid-infrared spectral range was investigated. The forward model employed in this study is a part of an algorithm used to retrieve trace gas profiles from high-resolution ground-based solar absorption Fourier transform infrared (FTIR) spectra, however, the results have general applicability. A finely spaced retrieval grid was constructed and made progressively more sparse in the troposphere and in the stratosphere. The effect was quantified in terms of transmission differences with respect to the most fine discretization for a suite of molecules (H₂O, O₃, CO, CO₂, CH₄, N₂O, NO, NO₂, HCl, HF, HNO₃, ClONO₂, and N₂) in microwindows commonly used in FTIR spectroscopy. Systematic differences in modeled transmissions are apparent when coarser grid schemes are used for all species and microwindows, though some are below random noise levels typical of spectra recorded at Toronto. The most significant are H₂O and O₃ at 0.30-0.73% and 0.10-0.34%, respectively. CO (0.13%), ClONO₂ (0.84%), and HF (1.03%) are also influenced by the interference of H₂O, which is sensitive to temperature interpolation errors via the lower state energy of the particular H₂O transition. O₃ is a significant interference in CO (0.42%) and ClONO₂ (0.31%) microwindows, but its influence is felt primarily via interpolation errors in the O₃ number concentration profile introduced by the coarser grids. HCl and HF themselves show the next most significant response in transmission to coarser stratospheric grids (∼0.18%). Finally, considering transmission differences >0.1% as significant in typical measurements, we identify maximum tropospheric and stratospheric layer widths that still lead to negligible transmission errors as, respectively, 0.6 and 2.0 km. These numbers can vary depending on the band or transition of interest, the signal-to-noise ratio of the measurement and the use of significantly different a priori volume mixing ratio profiles.     

Sensitivity of trace gas abundances retrievals from infrared limb emission spectra to simplifying approximations in radiative transfer modelling

The accuracy of trace gas abundances retrieved from spectrally resolved infrared limb emission measurements relies, among other things, on the appropriate modelling of radiative transfer through the actual atmosphere. We quantify the mapping of several commonly applied simplifications in radiative transfer modelling on the trace gas abundances retrieval error at the example of the Michelson interferometer for passive atmospheric sounding (MIPAS)/environmental satellite (ENVISAT) space borne Fourier transform infra-red limb emission experiment. The Karlsruhe optimized and precise radiative transfer algorithm (KOPRA) which was used as a tool for this study will be introduced. KOPRA supports accurate modelling of the particular instrument requirements of MIPAS and the observation scenarios during the ENVISAT mission, in particular with respect to its viewing direction and its altitude coverage of the atmosphere. We show that disregarding of horizontal temperature inhomogeneities and non-local thermodynamic equilibrium effects, insufficient accuracy in modelling of field-of-view and apodisation effects, and disregarding individual profiles of isotopic species play the key roles in radiative transfer modelling and lead to systematic retrieval errors which can by far exceed the expected random retrieval error caused by measurement noise.     

Analysis of the high-resolution infrared spectrum of cyclopropane

The high-resolution infrared spectrum of cyclopropane (C₃H₆) has been measured from 100 cm⁻¹ to 2200 cm⁻¹. In that region we have identified 24 absorption bands attributed to six fundamental bands, five combination bands, three hot bands and 10 difference bands. Long pathlength spectra, up to 32 m, facilitated the identification and analysis of many previously unstudied infrared inactive, and Raman and infrared inactive vibrational states, including direct access to two forbidden fundamental states, ν₄ and ν₁₄. An improved set of constants for the ground vibrational state as well as for the fundamental vibrations ν₇, ν₉, ν₁₀, ν₁₁ are also reported. The spectral resolution of the measurements varied from 0.002 cm⁻¹ to 0.004 cm⁻¹.     

Adjoint sensitivity analysis of radiative transfer equation: 2. Applications to retrievals of temperature in scattering atmospheres in thermal IR

An approach to formulation of inversion algorithms for thermal sounding in the case of scattering atmosphere based on the adjoint equation of radiative transfer (Ustinov, JQSRT 68 (2001) 195, referred to as Paper 1 in the main text) is applied to temperature retrievals in the scattering atmosphere for the nadir viewing geometry. Analytical expressions for the weighting functions involving the integration of the source function are derived. Temperature weighting functions for a simple model of the atmosphere with scattering are evaluated and convergence to the case of pure atmospheric absorption is demonstrated. The numerical experiments on temperature retrievals are carried out to demonstrate the validity of the expressions obtained.     

Fourier transform infrared emission spectra of MnH and MnD

Fourier transform infrared emission spectra of MnH and MnD were observed in the ground X⁷Σ⁺ electronic state. The vibration-rotation bands from v = 1 → 0 to v = 3 → 2 for MnH and from v = 1 → 0 to v = 4 → 3 for MnD were recorded at an instrumental resolution of 0.0085 cm⁻¹. Spectroscopic constants were determined for each vibrational level and equilibrium constants were found from a Dunham-type fit. The equilibrium vibrational constant (ω_e) for MnH was found to be 1546.84518(65) cm⁻¹, the equilibrium rotational constant (B_e) is 5.6856789(103) cm⁻¹ and the eqilibrium bond distance (r_e) was determined to be 1.7308601(47) Å.     

Intercomparison of retrieval codes used for the analysis of high-resolution, ground-based FTIR measurements

A rigorous and systematic intercomparison of codes used for the retrieval of trace gas profiles from high-resolution ground-based solar absorption FTIR measurements is presented for the first time. Spectra were analyzed with the two widely used independent, retrieval codes: SFIT2 and PROFFIT9. Vertical profiles of O₃, HNO₃, HDO, and N₂O were derived from the same set of typical observed spectra. Analysis of O₃ was improved by using updated line parameters. It is shown that profiles and total column amounts are in excellent agreement, when similar constraints are applied, and that the resolution kernel matrices are also consistent. Owing to the limited altitude resolution of ground-based observations, the impact of the constraints on the solution is not negligible. It is shown that the results are also compatible for independently chosen constraints. Perspectives for refined constraints are discussed. It can be concluded that the error budget introduced by the radiative transfer code and the retrieval algorithm on total columns deduced from high-resolution ground-based solar FTIR spectra is below 1%.     

Infrared and near infrared emission spectra of TeH and TeD

The vibration-rotation emission spectra for the X²Π ground state and the near infrared emission spectra of the X²Π_1/2-X²Π_3/2 system of the TeH and TeD free radicals have been measured at high resolution using a Fourier transform spectrometer. TeH and TeD were generated in a tube furnace with a DC discharge of a flowing mixture of argon, hydrogen (or deuterium), and tellurium vapor. In the infrared region, for the X²Π_3/2 spin component we observed the 1-0, 2-1, and 3-2 vibrational bands for most of the eight isotopologues of TeH and the 1-0 and 2-1 bands for three isotopologues of TeD. For the X²Π_1/2-X²Π_3/2 transition, we observed the 0-0 and 1-1 bands for TeH and the 0-0, 1-1, and 2-2 bands for TeD. Except for a few lines, the tellurium isotopic shift was not resolved for the X²Π_1/2-X²Π_3/2 transitions of TeH and TeD. Local perturbations with Δv = 2 between the two spin components of the X²Π state of TeH were found: X²Π_1/2, v = 0 with X²Π_3/2, v = 2; X²Π_1/2, v = 1 with X²Π_3/2, v = 3. The new data were combined with the previous data from the literature and two kinds of fits (Hund’s case (a) and Hund’s case (c)) were carried out for each of the 10 observed isotopologues: ¹³⁰TeD, ¹²⁸TeD, ¹²⁶TeD, ¹³⁰TeH, ¹²⁸TeH, ¹²⁶TeH, ¹²⁵TeH, ¹²⁴TeH, ¹²³TeH, and ¹²²TeH.     

Atmospheric weighting functions and surface partial derivatives for remote sensing of scattering planetary atmospheres in thermal spectral region: general adjoint approach

An approach to formulation of inversion algorithms for remote sensing in the thermal spectral region in the case of a scattering planetary atmosphere, based on the adjoint equation of radiative transfer (Ustinov (JQSRT 68 (2001) 195; JQSRT 73 (2002) 29); referred to as Papers 1 and 2, respectively, in the main text), is applied to the general case of retrievals of atmospheric and surface parameters for the scattering atmosphere with nadir viewing geometry. Analytic expressions for corresponding weighting functions for atmospheric parameters and partial derivatives for surface parameters are derived. The case of pure atmospheric absorption with a scattering underlying surface is considered and convergence to results obtained for the non-scattering atmospheres (Ustinov (JQSRT 74 (2002) 683), referred to as Paper 3 in the main text) is demonstrated.     

Analysis of high-resolution infrared and CARS spectra of SO3

Three fundamental modes and several hot bands of ³⁴S¹⁸O₃ have been investigated using both infrared spectroscopy and coherent anti-Stokes Raman scattering spectroscopy (CARS). Coriolis coupling effects are particularly noticeable in ³⁴S¹⁸O₃ due to the close proximity of the ν₂ and ν₄ fundamental vibrations, whose wavenumber values are 477.50864(5) and 502.05565(4) cm⁻¹. The uncertainties in the last digits are shown in parentheses and are two standard deviations. Hot band transitions from ν₂, ν₄ levels give access to infrared inactive ν₂, ν₄ combination/overtone levels which interact strongly with levels of the Raman-active ν₁ symmetric stretching mode due to indirect Coriolis couplings, l-resonances, and Fermi resonances. The result is a complex ν₁ CARS Q-branch spectrum that is the most perturbed of the four SO₃ isotopomers we have studied. The relative importance of these interaction terms on the ν₁ CARS spectrum is examined in some detail and accurate rovibrational constants are determined for all of the mixed states, leading to deperturbed values of 1004.662(24), 0.0003503(9), and 0.0007066(12) cm⁻¹ for ν₁, α₁^B, and α₁^C, respectively. The B_e value is found to be 0.310875(12) cm⁻¹, which gives an equilibrium bond length r_e of 141.7339(3) pm, in excellent agreement with values of 141.7340(1) and 141.7347(7) pm reported earlier for ³²S¹⁶O₃ and ³⁴S¹⁶O₃.     

Infrared and near infrared emission spectra of SbH and SbD

The X³Σ⁻ ground state vibration-rotation spectrum of SbH and the near infrared spectra of the b¹Σ⁺-X³Σ⁻ transitions of SbH and SbD have been measured at high resolution by Fourier transform spectroscopy. The SbH and SbD radicals were generated in a tube furnace with a D.C. discharge of a flowing mixture of argon, hydrogen (or deuterium), and antimony vapor. In the infrared region, the 1-0 and 2-1 bands of the three components (0⁺, 1_e, and 1_f) as well as the 0⁺ component of the 3-2 band were observed for ¹²¹SbH and ¹²³SbH. In the near infrared region, the 0-0, 1-1, and 2-2 bands of the b¹Σ⁺-X³Σ⁻ system of both SbH and SbD as well as the 3-3 band of SbD were observed. Except for a few lines, the antimony isotopic shift was not resolved for these electronic spectra. The present data set was combined with the available ground state data on SbD and a¹Δ data for SbH and SbD from previous work, and a least-squares fit was performed for each of the four isotopologues: ¹²¹SbH, ¹²³SbH, ¹²¹SbD, and ¹²³SbD. Improved spectroscopic constants were obtained for the observed vibrational levels of the X³Σ⁻, a¹Δ, and b¹Σ⁺ states of these four isotopologues. In addition, all the above data were also fitted simultaneously to a multi-isotopologue Dunham model, which yielded Dunham constants and Born-Oppenheimer breakdown parameters for these three electronic states. Interestingly, we found that Born-Oppenheimer breakdown corrections were also required for some of the spin-spin and spin-rotation parameters of the X³Σ⁻ state.     

气泡数密度对尾流光束衰减测量的影响

为准确地测量出尾流气泡群的衰减,提高前向光尾流探测的可靠性,研究了气泡数密度对尾流光束衰减测量的影响.基于辐射传输方程的小角度近似解,得到了探测截面上的约化功率和漫射功率的表达式.根据测量条件,引入了有尾流气泡和无尾流气泡时探测截面上接收到的辐射功率之比作为透射函数,并进一步引进了复散射校正因子,它表征了复散射效应的强弱.针对典型的尾流气泡分布,通过数值计算得到了不同测量条件下气泡数密度与复散射校正因子、透射函数的关系.数值计算结果表明：复散射校正因子都随气泡数密度的增大单调的增大,透射函数都随气泡数密度的增大单调的减小;测量条件不同,气泡数密度对光束衰减的影响也不同.研究结果表明,给定测量条件和透射比时,利用小角度辐射方程可以得到气泡群数密度的量化信息.     

Analytic evaluation of the weighting functions for remote sensing of blackbody planetary atmospheres: a general linearization approach

An analytic approach is proposed for the evaluation of weighting functions for remote sensing of a blackbody planetary atmosphere based on straightforward, general linearization. In the present paper, this approach is applied to the case of remote sensing with the nadir (down-looking) geometry. Expressions for weighting functions for various atmospheric parameters are derived. It is demonstrated that in a realistic case of temperature-dependent atmospheric absorption, an additional term appears in the expression for the temperature weighting function which contains the temperature derivative of the atmospheric absorption coefficient. The approach is applied to the case of a semi-infinite atmosphere and then, to the atmosphere of a finite optical depth with the underlying surface. In this, latter case, the expressions are also obtained for partial derivatives of observed radiances with respect to surface parameters: surface pressure, temperature and emissivity.     

Substitution structure of cyanogen, NCCN, from high-resolution far infrared spectra

The lowest lying vibrational bands of the gas-phase spectra of cyanogen, NCCN, and four of its isotopomers, , , , and , were recorded with a Fourier transform interferometer. The resolution was limited by the maximum optical path difference (MOPD) attainable with the interferometer to . Rovibrational transitions of the ν₅ () and also the ν₂-ν₅ () band systems were assigned for all five isotopomers. The use of an effective Hamiltonian for linear molecules to fit the data yielded precise spectroscopic vibrational and rotational constants for the vibrational states (v₁v₂v₃v₄v₅) or (v₄v₅)=(00), (01), (02), (03), and (01000). These data include the first rotationally resolved transitions involving (01000). Complete substitution (r_s) structures of cyanogen, based on both single and double isotopic substitution of the parent species, were calculated. The derived structure is r_CC=138.48(17) pm and r_CN=115.66(13) pm. The two r_s structures coincide within the errors due to remaining contributions of zero-point vibrations.     

Evolution of infrared spectra and optical emission spectra in hydrogenated silicon thin films prepared by VHF-PECVD

A series of hydrogenated silicon thin films with varying silane concentrations have been deposited by using very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) method. The deposition process and the silicon thin films are studied by using optical emission spectroscopy (OES) and Fourier transfer infrared (FTIR) spectroscopy, respectively. The results show that when the silane concentration changes from 10% to 1%, the peak frequency of the Si—H stretching mode shifts from 2000 cm ^{- 1} to 2100 cm ^{- 1}, while the peak frequency of the Si—H wagging—rocking mode shifts from 650 cm ^{- 1} to 620 cm ^{- 1}. At the same time the SiH^*/H_α intensity ratio in the plasma decreases gradually. The evolution of the infrared spectra and the optical emission spectra demonstrates a morphological phase transition from amorphous silicon (a-Si:H) to microcrystalline silicon (μc-Si:H). The structural evolution and the μc-Si:H formation have been analyzed based on the variation of H_α and SiH^* intensities in the plasma. The role of oxygen impurity during the plasma process and in the silicon films is also discussed in this study.     

Radiative intensity solution and thermal emission analysis of a semitransparent medium layer with a sinusoidal refractive index

The radiative intensity in a sinusoidal refractive index semitransparent medium layer is solved by the curved ray-tracing method in combination with the pseudo-source adding method. One boundary of the medium layer is an opaque diffuse substrate wall. The other boundary is a semitransparent specular or diffuse surface, from which the medium thermal emission emerges. With considering a linear temperature distribution, the radiative intensity formulae are, respectively, deduced under the two boundary conditions. On the basis of the radiative intensity solutions, the directional and hemispherical emission of the medium layer with a specular surface as well as the hemispherical emission of that with a diffuse surface are calculated. The influences of the optical thickness, sinusoidal refractive index distribution and linear temperature distribution on the thermal emission are investigated. The results show that the effects of refractive index and temperature distribution are significant and are different under the two reflecting modes of the surface.     

Study on the impact of polar stratospheric clouds on high resolution mid-IR limb emission spectra

Satellite observations of polar stratospheric clouds (PSCs) in the mid-infrared by high resolution limb emission spectrometers like the Michelson Interferometer for Passive Atmospheric Sounding have been simulated. For particles with radius the scattered tropospheric radiance accounts for a significant part of the continuum signal and leads to absorption line features overlaid over the stratospheric emission spectrum. The scattered radiance shows a strong dependence on particle size up to about radius with a maximum around 3-4. The contribution of scattered radiation depends heavily on tropospheric cloud coverage and earth surface temperature. Distinction of PSCs of different composition is possible for small particles due to differences in the imaginary part of the refractive index. For particles with radii between 1 and the simulated spectra for various PSC compositions differ due to different real parts of the refractive index. For larger particles no distinction is possible any more. Solar radiance scattered by PSCs is important for wavenumbers larger than about . For a forward scattering geometry with 30° between the position of the sun and the limb viewing direction solar contribution exceeds the terrestrial scattered radiation by about a factor of 10.     

Measurements of mid-stratospheric formaldehyde from the Odin/SMR instrument

Measurements of mid-stratospheric formaldehyde (H₂CO) have been obtained from the limb-viewing sub-millimeter radiometer (SMR) instrument aboard the Odin satellite. The analysis is based upon the only weak (8₀₈→7₀₇) rotational transition line of H₂CO that can be measured by Odin/SMR at 576.7083150 GHz in the band dedicated to the measurement of carbon monoxide (CO). The signal-to-noise ratio is increased by averaging about 1000 spectra within 2-km width vertical layers in the stratosphere over periods from 1 to 7 days and within 3 latitude bands: Southern Hemisphere (90°S-45°S), tropics (30°S-30°N), and Northern Hemisphere (45°N-90°N). The faint H₂CO line can then be retrieved using the standard scientific ground-segment developed for the Odin/SMR measurements. The mid-stratospheric H₂CO shows maxima in the tropics for every period considered (January 2006, February 2005, March 2005, and September 2005). The spring-time extra-tropical mid-stratospheric H₂CO is more intense than the fall-time extra-tropical amounts. The simulations from the three-dimensional chemical-transport model Reprobus satisfactorily show these general features.