Millimeter and submillimeter wave absorption by atmospheric pollutants and constituents

Calculated absorption coefficients and rotational transition frequencies ara given for a number of polar molecules of interest to pollution and energy research. The results, which are presented in graphical form for microwave frequencies up to 1400 GHz, illustrate the increased absorption line intensities occurring in the submillimeter region. For most species, these absorption coefficients attain their maximum values in this region. Included in the calculations are SO₂, H₂CO, O₃, H₂O, H₂S, OCS, CO, NO, OH, SO, NH₃, and CS. A discussion of the techniques currently available for detection in the submillimeter region of these species is also given.     

Multi-species laser absorption sensors for in situ monitoring of syngas composition

Tunable diode laser absorption spectroscopy sensors for detection of CO, CO₂, CH₄ and H₂O at elevated pressures in mixtures of synthesis gas (syngas: products of coal and/or biomass gasification) were developed and tested. Wavelength modulation spectroscopy (WMS) with 1f-normalized 2f detection was employed. Fiber-coupled DFB diode lasers operating at 2325, 2017, 2290 and 1352 nm were used for simultaneously measuring CO, CO₂, CH₄ and H₂O, respectively. Criteria for the selection of transitions were developed, and transitions were selected to optimize the signal and minimize interference from other species. For quantitative WMS measurements, the collision-broadening coefficients of the selected transitions were determined for collisions with possible syngas components, namely CO, CO₂, CH₄, H₂O, N₂ and H₂. Sample measurements were performed for each species in gas cells at a temperature of 25 °C up to pressures of 20 atm. To validate the sensor performance, the composition of synthetic syngas was determined by the absorption sensor and compared with the known values. A method of estimating the lower heating value and Wobbe index of the syngas mixture from these measurements was also demonstrated.     

Millimeter and sub-millimeter wave detection of hydrogen peroxide

The measurement of small concentrations of hydrogen peroxide through the detection of rotational transitions in the millimeter and sub-millimeter wave regions is discussed. Calculated transition frequencies and absorption coefficients of H₂O₂ for frequencies up to 2000 GHz are presented. The reliability of the calculated values is illustrated by measurements of the linewidths and absorption coefficients of transitions in the 140 GHz range. Finally, methods for the detection of trace quantities of the peroxide molecule are briefly described.     

Optical properties of clusters and molecules from real-time time-dependent density functional theory using a self-consistent field

We present a detailed study of optical absorption spectra of finite-size structures, using a method based on time-dependent density-functional theory (TDDFT), which involves a self-consistent field for the propagation of the Kohn–Sham wavefunctions in real-time. Although our approach does not provide a straightforward assignment of absorption features to corresponding transitions between Kohn–Sham orbitals, as is the case in frequency-domain TDDFT methods, it allows the use of larger timesteps while conserving total energy and maintaining stable dipole moment oscillations. These features enable us to study larger systems more efficiently. We demonstrate the efficiency of our method by applying it to a hydrogen-terminated silicon cluster consisting of 364 atoms, with and without P impurities. For cases where direct comparison to experiment can be made, we reproduce the absorption features of fifteen small molecules [N₂, O₂, O₃, NO₂, N₂O, NH₃, H₂O, H₂CO, H₂CO₃, CO₂, CH₄, C₂H₂, C₂H₄, C₂H₆, C₆H₆] and find generally good agreement with experimental measurements. Our results are useful for the detection and the determination of orientation of these molecules.     

The rotationally-resolved absorption spectrum of formaldehyde from 6547 to 6804 cm

The room temperature absorption spectrum of formaldehyde, H₂CO, from 6547 to 6804 cm⁻¹ (1527-1470 nm) is reported with a spectral resolution of 0.001 cm⁻¹. The spectrum was measured using cavity-enhanced absorption spectroscopy (CEAS) and absorption cross-sections were calculated after calibrating the system using known absorption lines of H₂O and CO₂. Several vibrational combination bands occur in this region and give rise to a congested spectrum with over 8000 lines observed. Pressure broadening coefficients in N₂, O₂, and H₂CO are reported for an absorption line at 6780.871 cm⁻¹, and in N₂ for an absorption line at 6684.053 cm⁻¹.     

Analytical representation of broadening coefficients of vibrational-rotational absorption lines of linear molecules

Analytical formulas are proposed for the coefficients that determine broadening of vibrational-rotational absorption lines of diatomic and linear molecules in the case when the broadening is caused by the pressure of buffer gases or linear molecules. The formulas are obtained by the parameterization of the semiclassical method relations with allowance for the predominant contribution related to polarization or dipole-quadrupole interaction. The parameters of the analytical formulas are determined for different vibrational bands of HCl and HF molecules in the case of argon, nitrogen, and air broadening, as well as for CO and CO₂ molecules in the case of broadening by collisions with CO, CO₂, N₂, O₂, and H₂O.     

The absorption cross sections of N2, O2, CO,NO, CO2, N2O,CH4, C2H4, C2H6 and C4H10 from 180 to 700Å

The absorption cross sections of N₂, O₂, CO, NO, CO₂, N₂O, CH₄, C₂H₄, C₂H₆, C₄H₁₀ have been measured photoelectrically in the 180–700 Å region using synchrotron radiation. The absorption cross sections in the region λ ≥ 500 Å was found to be structureless and to increase monotonically with wavelength for all gases. The positions of the structure observed in the 520–720 Å region for N₂, O₂, CO₂ and N₂O are consistent with the various Rydberg series reported by previous authors.     

Scanned-wavelength-modulation spectroscopy near 2.5 μm for H2O and temperature in a hydrocarbon-fueled scramjet combustor

The design and demonstration of a two-color tunable diode laser sensor for measurements of temperature and H₂O in an ethylene-fueled model scramjet combustor are presented. This sensor probes multiple H₂O transitions in the fundamental vibration bands near 2.5 μm that are up to 20 times stronger than those used by previous near-infrared H₂O sensors. In addition, two design measures enabled high-fidelity measurements in the nonuniform flow field. (1) A recently developed calibration-free scanned-wavelength-modulation spectroscopy spectral-fitting strategy was used to infer the integrated absorbance of each transition without a priori knowledge of the absorption lineshape and (2) transitions with strengths that scale near-linearly with temperature were used to accurately determine the H₂O column density and the H₂O-weighted path-averaged temperature from the integrated absorbance of two transitions.     

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.     

Satellite peaks in the high energy photoelectron spectra of some small first row molecules

The gas phase high energy photoelectron spectra of CH₄, NH₃, H₂O, N₂, O₂, CO and CO₂ have been recorded, and in all cases weak satellite peaks to high binding energy of the main ionization peak are observed. These peaks are assigned to transitions to ionic states in which valence electron excitation as well as core ionization has occurred. The intensity and position of these peaks, relative to the main ionization peak have been estimated from ab initio UHF calculations on the core hole states, which in general allow assignment of the satellite peaks in terms of orbital transitions of the core hole ion.     

Anomalous absorption in H<Subscript>2</Subscript>CN and CH<Subscript>2</Subscript>CN molecules

Structures of H₂CN and CH₂CN molecules are similar to that of H₂CO molecule. The H₂CO has shown anomalous absorption for its transition 1₁₁–1₁₀ at 4.8 GHz in a number of cool molecular clouds. Though the molecules H₂CN and CH₂CN have been identified in TMC-1 and Sgr B2 through some transitions in ortho as well as in para species, here we have investigated the condition under which transitions 1₁₁–1₁₀ and 2₁₂–2₁₁ of these molecules may show anomalous absorption. For the present investigation, we have calculated energy levels and radiative transition probabilities. However, we have used scaled values for collisional rate coefficients. We found that relative values of collisional rate coefficients can produce the required anom-alous absorption in 1₁₁–1₁₀ and 2₁₂–2₁₁ transitions in the molecules.      

Mott insulator-superfluid phase transition in p-band triangle optical lattices with on-site rotation

In order to exploit the potential applications of graphene as gas sensors, the adsorptions of a series of small gas molecules (such as CO, O₂, NO₂ and H₂O) on pristine graphene (PG) and Si-doped graphene (SiG) have been investigated by ab initio calculations. Our results indicate that the electronic properties of PG are sensitive to O₂ and NO₂ molecules, but not changed much by the adsorption of CO and H₂O molecules. Compared with PG, SiG is much more reactive in the adsorption of CO, O₂, NO₂ and H₂O. The strong interactions between SiG and the adsorbed molecules induce dramatic changes to the electronic properties of SiG. Therefore, we suggest that SiG could be a good gas sensor for CO, O₂, NO₂ and H₂O.     

Diode laser absorption spectroscopy measurement of linestrengths and pressure broadening coefficients of the methane 2ν3 band at elevated temperatures

A diode laser sensor based on absorption spectroscopy has been developed for the measurement of spectroscopic parameters in the R (3) and R (4) manifolds of 2ν₃ band of CH₄. Individual linestrengths of each transition are determined for a range of temperatures. In addition, collision-broadened half-widths for CO₂, N₂, H₂O, CH₄, and CO collision partners are measured as a function of temperature and pressure for these strongly overlapped transitions. From this, temperature dependence of the collision half-width for each collision partner is determined. Using a new method for calculation of collisional broadening at high temperatures for strongly overlapped transitions makes these transitions accessible for spectroscopy.     

A mid-infrared scanned-wavelength laser absorption sensor for carbon monoxide and temperature measurements from 900 to 4000 K

Mid-infrared laser absorption sensors based on quantum cascade laser (QCL) technology offer the potential for high-sensitivity, selective, and high-speed measurements of temperature and concentration for species of interest in high-temperature environments, such as those found in combustion devices. A new mid-infrared QCL absorption sensor for carbon monoxide and temperature measurements has been developed near the intensity peak of the CO fundamental band at 4.6 μm, providing orders-of-magnitude greater sensitivity than the overtone bands accessible with telecommunications lasers. The sensor is capable of probing the R(9), R(10), R(17), and R(18) transitions of the CO fundamental ro-vibrational band which are located at frequencies where H₂O and CO₂ spectral interference is minimal. Temperature measurements are made via scanned-wavelength two-line ratio techniques using either the R(9) and R(17) or the R(10) and R(18) line pairs. The high-speed (1–2 kHz) scanned-wavelength sensor is demonstrated in room-temperature gas cell measurements of CO and, to demonstrate the potential of the sensor for high-temperature thermometry, in shock-heated gases containing CO for a very wide range of temperature (950–3500 K) near 1 atm. To our knowledge, these measurements represent the first use of QCL-based absorption sensor for thermometry at elevated combustion-like temperatures. The high-temperature measurements of CO mole fraction and temperature agree with the post-reflected-shock conditions within ±1.5% and ±1.2% (1σ deviation), respectively.     

Diode laser measurements of temperature-dependent collisional-narrowing and broadening parameters of Ar-perturbed H2O transitions at 1391.7 and 1397.8 nm

High-resolution absorption lineshapes of two H₂O transitions near 7185.60 and 7154.35 cm⁻¹ have been recorded in a heated static cell as a function of temperature (296-1100 K) and pressure (6-830 Torr) using two distributed-feedback diode lasers. The measured absorption spectra are least squares fit to both Voigt and Galatry profiles. Strong collisional-narrowing effects are observed in the Ar-broadened H₂O spectra at near-atmospheric pressure due to the relatively weak collisional broadening induced by Ar-H₂O collisions, while collisional narrowing is not significant for pure H₂O absorption lineshapes. Line strengths and self-broadening coefficients are inferred from the pure H₂O absorption spectra and compared with published data. Temperature dependences of the Ar-induced broadening, narrowing, and shift coefficients are determined using Galatry fits to the absorption data. The measured collisional-narrowing parameters have similar temperature dependence to the collisional-broadening coefficients.     

Absorption coefficients of sulfur dioxide microwave rotational lines

New calculations of the absorption coefficients of the rotational transitions of ³²S¹⁶O₂ are given for all energy levels up to J = 50 and frequencies less than 200 GHz. A spectrometer incorporating a semiconfocal Fabry-Perot resonant cavity and operating in the vicinity of 70 GHz is described. The calculated absorption coefficients are compared to measured values obtained with this spectrometer and to existing measurements over the frequency range 26–40 GHz. The results obtained are in general agreement to within 5–10%. A detailed knowledge of the absorption coefficient behavior as a function of frequency is of particular interest in the development of high-sensitivity SO₂ monitors, and in investigations of the kinetics of fast chemical reactions.     

Intrapulse quantum cascade laser spectroscopy: pressure induced line broadening and shifting in the ν 6 band of formaldehyde

A rapidly swept quantum cascade laser (QCL) has been used to probe a small region of the ν ₆ band of formaldehyde around 8 μm by direct absorption spectroscopy. Two of the strongest transitions accessible within the operating region of the QCL are assigned as (1,1,1)←(2,0,2) and (10,1,9)←(9,2,8). In this paper, we report pressure-induced broadening and shift coefficients for these transitions with a variety of gases (He, Ne, Kr, Ar, N₂, O₂, and CO₂). The pressure broadening coefficient measurements are shown (in some cases) to be chirp rate dependent, even under conditions where rapid passage effects are negligible, highlighting the marked difference that can occur between studies with rapidly swept fields and those employing conventional diode laser devices.     

The structure and vibrational spectral parameters of a complex of HF with the planar (H<Subscript>2</Subscript>CO)<Subscript>2</Subscript> dimer

Equilibrium nuclear configurations of the planar formaldehyde homodimer (H₂CO)₂ and the (H₂CO)₂···HF complex are determined in the MP2/6-311++G(3df, 3pd) approximation taking into account the superposition error of basis sets of monomers. Harmonic values of the frequencies and intensities of fundamental transitions between vibrational states of these hydrogen-bonded complexes were calculated using the Gaussian 09 package of programs. Anharmonic values of the frequencies and intensities of the ν(H–F) stretching vibration and several intermolecular vibrations in the (H₂CO)₂···HF trimer were obtained from variational solutions of one-, two-, and three-dimensional vibrational Schrödinger equations. The anharmonic influence of the C=O and hydrogen bond O···H–F stretching vibrations, as well as of librational vibrations of monomers, on the spectral parameters of the strongest ν(H–F) absorption band of trimer was studied.     

Vibrational moments of fundamental transitions in low-temperature molecular liquids: Determination from the band shape of vibrations in the overtone spectral range

It is shown that the integrated absorption coefficients of strong fundamental bands of some gaseous substances can be determined with an accuracy of 5–10% using experimental data on the spectral moments of bands in the overtone spectral range of these substances in the liquid phase near the melting point. The absorption coefficients are calculated within the framework of the cell model of the liquid state from the contributions of the resonance dipole-dipole interaction to the second spectral moment. The combination and overtone absorption bands of the SF₆, CF₄, SiF₄, NF₃, CHF₃, CC1F₃, CBrF₃, OCS, N₂O, and CO₂ molecules in the liquid state and in solutions in liquefied Xe, Kr, and O₂ are recorded. The data in the literature on the intensity of strong IR bands in the gas phase are analyzed. Using an improved experimental technique, additional measurements are performed. It is found that the absorption coefficients determined from the spectral characteristics of the liquids agree well with the coefficients measured in the gas phase.     

Vibrational study of H3OUO2PO4 · 3 H2O (HUP) and related compounds. phase transitions and conductivity mechanisms: part I,KUO2PO4 · 3 H2O (KUP)

Infrared and Raman spectra of polycrystalline KUO₂PO₄ · 3 H₂O (KUP) and its isotopic derivatives KUO₂P¹⁸O₄ · 3 H₂O and KUO₂PO₄ · 3 D₂O have been investigated in the 4000-10-cm^?1 range at different temperatures. An assignment of the bands in terms of UO₂, PO₄ and H₂O vibrations has been proposed. Combined differential scanning calorimetry and spectroscopic data show two diffuse phase transitions near 130 and 230 K. Comparison of the vibrational spectra of phase I at 300 K and phase IV at 100 K indicates that ordering of the water molecules with subsequent ordering of PO₄ tetrahedra on a site with lower symmetry appears to be the main mechanism responsible for the phase transformation. All the six O-H distances of water molecules in phase IV are found to be crystallographically nonequivalent. Conducting ion frequencies and the corresponding force constants have been determined for the analogous compounds MUP with M = K⁺, Na⁺, Ag⁺, NH⁺₄, Tl⁺ and H₃O⁺ and compared with other properties of these ionic conductors. Conductivity mechanisms in these materials are discussed.