Fourier Transform Emission Spectroscopy of CuCl

The electronic spectra of CuCl were observed in the 18 000 cm(-1) to 25 000 cm(-1) spectral region using a Bruker IFS 120 HR Fourier transform spectrometer (FTS) and with the FTS associated with the McMath-Pierce Solar Telescope at Kitt Peak. On the basis of ab initio calculations, the labels for the electronic states were revised, and the a(3)Sigma(+)(1)-X(1)Sigma(+) 0-0 band, the b(3)Pi(0)-X(1)Sigma(+) 0-0, 1-0, and 0-1 bands, the b(3)Pi(1)-X(1)Sigma(+) 0-0, 1-0, and 0-1 bands, the A(1)Pi-X(1)Sigma(+) 0-0, 1-0, and 0-2 bands, and the B(1)Sigma(+)-X(1)Sigma(+) 0-0 and 1-0 bands were measured. Improved spectroscopic constants were obtained for the excited and ground states. Copyright 2001 Academic Press.     

Laser-Induced Fluorescence and Fourier Transform Spectroscopy of NiCl: Identification of a Low-Lying (2)Sigma(+) State (1768 cm(-1))

From a comparison with the spectrum of NiF, a low-lying (2)Sigma(+) state is expected to lie in the first 2000 cm(-1) above the ground X(2)Pi(3/2) state of NiCl. The identification of this (2)Sigma(+) (v = 0) state (at 1768 cm(-1)) has been carried out through the analysis of two electronic transitions (2)Pi(3/2)-(2)Sigma(+) (22 720 cm(-1)) and (2)Pi(1/2)-(2)Sigma(+) (23 210 cm(-1)) recorded by high-resolution Fourier transform spectroscopy. Dispersed fluorescence spectroscopy allowed these transitions to be located on an absolute energy-level diagram that includes the previously studied electronic states. Copyright 2000 Academic Press.     

Fourier Transform Spectroscopy of Chemiluminescence from the SrO A(1)Sigma(+)-X(1)Sigma(+) Transition

The A(1)Sigma(+)-X(1)Sigma(+) chemiluminescence spectrum of SrO was observed using a Fourier transform spectrometer. SrO was produced in a Broida-type oven from the Sr + N(2)O reaction. A total of 75 bands from (88)SrO, (87)SrO, and (86)SrO were measured in the range of 7600-13 600 cm(-1) at a resolution of 0.04 cm(-1). The vibrational levels of the ground state were observed up to v" = 12 and over 10 000 rovibrational lines with J as high as 153 were analyzed at a precision of about 0.005 cm(-1). Significantly improved spectral constants for the ground state were obtained by representing the perturbed excited state by term values and by adding the known microwave data and infrared data to our fit. Strong perturbations were observed in the upper A state. The vibrational levels of the A(1)Sigma(+) state were measured up to v' = 8 and some new perturbations are reported. Copyright 2000 Academic Press.     

Fourier Transform Infrared Emission Spectroscopy of SeH

The infrared vibration-rotation bands of SeH have been measured in the X(2)Pi ground state using a Fourier transform spectrometer. The bands were observed in a microwave discharge of a mixture of H(2) and Se in the presence of He. The rotational structure of the 1-0, 2-1, 3-2 bands of the X(2)Pi(3/2) spin component and the 1-0 band of X(2)Pi(1/2) spin component has been observed in the 1800-2600 cm(-1) region. The principal ground state molecular constants obtained are omega(e) = 2421.7153(234) cm(-1), omega(e)x(e) = 44.6012(110) cm(-1), omega(e)y(e) = 0.20697(236) cm(-1), B(e) = 7.899187(696) cm(-1), alpha(e) = 0.220749(399) cm(-1), and r(e) = 1.464319(64) ?. This work is the first determination of the equilibrium molecular constants of the X(2)Pi state of SeH. Copyright 2000 Academic Press.     

Analysis of high temperature ammonia spectra from 780 to 2100 cm

A recently-recorded set [Hargreaves et al., Astrophys. J., in press] of Fourier transform emission spectra of hot ammonia is analyzed using a variational line list. Approximately 3350 lines are newly assigned to mainly hot bands from vibrational states as high as v₂ = 2. 431 new energy levels of these states are experimentally determined, considerably extending the range of known rotationally-excited states. Comparisons with a recent study of high J levels in the ground and first vibrational states [Yu et al., J. Chem. Phys., 133 (2010) 174317] suggests that while the line assignments presented in that work are correct, their energy level predictions suffer from problems associated with the use of very high-order perturbation series in the effective Hamiltonian. It is suggested that variational calculations provide a more stable method for analyzing spectra involving highly-excited states of ammonia.     

Infrared absorption cross-sections for acetaldehyde (CH3CHO) in the 3 μm region

A series of infrared absorption cross-sections for acetaldehyde has been measured in the 3 μm region from spectra obtained using a high-resolution Fourier transform spectrometer (Bruker IFS 125/HR). Results presented are for mixtures of acetaldehyde vapor combined with pure synthetic air taken at various temperatures and pressure to simulate atmospheric conditions found principally in the Earth's troposphere and lower stratosphere. Spectra were recorded at a resolution of 0.005 cm⁻¹ and intensities were calibrated using three acetaldehyde spectra (measured at 278, 298 and 323 K) provided by the Pacific Northwest National Laboratory (PNNL) IR database.     

Infrared absorption cross sections for acetone (propanone) in the 3 μm region

Infrared absorption cross sections for acetone (propanone), CH₃C(O)CH₃, have been determined in the 3 μm spectral region from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125 HR) and a multipass cell with a maximum optical path length of 19.3 m. The spectra of mixtures of acetone with dry synthetic air were recorded at 0.015 cm⁻¹ resolution (calculated as 0.9/MOPD using the Bruker definition of resolution) at a number of temperatures and pressures (50-760 Torr and 195-296 K) appropriate for atmospheric conditions. Intensities were calibrated using three acetone spectra (recorded at 278, 293 and 323 K) taken from the Pacific Northwest National Laboratory (PNNL) IR database.     

Acetonitrile (CH3CN) infrared absorption cross sections in the 3 μm region

High resolution infrared absorption cross sections of acetonitrile have been determined from spectra recorded in the 3 μm spectral region using a Bruker IFS 125 HR Fourier transform spectrometer (FTS) and a multipass White cell. The eleven synthetic air-broadened acetonitrile spectra were recorded at a resolution of 0.015 cm⁻¹ (calculated as 0.9/MOPD (Maximum Optical Path Difference), the Bruker definition of resolution) over a range of different temperatures and pressures that are representative of conditions in the Earth's atmosphere (50-760 Torr and 207-296 K). Intensities were calibrated using infrared spectra recorded at the Pacific Northwest National Laboratory (PNNL). These new cross sections will enable satellite retrievals of acetonitrile in the 3 μm region from atmospheric spectra recorded by satellite instruments, such as the ACE (Atmospheric Chemistry Experiment)-FTS.     

Direct fit of experimental ro-vibrational intensities to the dipole moment function: Application to HCl

A dipole moment function (DMF) for hydrogen chloride (HCl) has been obtained using a direct fit approach that fits the best available and appropriately weighted experimental data for individual ro-vibrational transitions. Combining wavefunctions derived from the Rydberg-Klein-Rees (RKR) numerical method and a semi-empirical DMF, line intensities were calculated numerically for bands with Δv=0, 1, 2, 3, 4, 5, 6, 7 up to v′=7. The results have demonstrated the effectiveness of inclusion of rotational dipole moment matrix elements and appropriate weighting of the experimental data in the DMF fitting. The new method is shown to be superior to the common method of fitting only the rotationless dipole moment elements, while at the same time being simple to implement.     

Trends in atmospheric halogen containing gases since 2004

The changes in the atmospheric concentration of 16 halogenated gases in the atmosphere have been determined using measurements made by the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS). ACE-FTS has been used to measure the change in concentration between 2004 and 2010 of CCl₄, CF₄, CCl₃F (CFC-11), CCl₂F₂ (CFC-12), C₂Cl₃F₃ (CFC-113), CH₃Cl, ClONO₂, COF₂, COCl₂, COClF, CHF₂Cl (HCFC-22), CH₃CCl₂F (HCFC-141b), CH₃CClF₂ (HCFC-142b), HCl, HF and SF₆ between 30°N and 30°S. ACE-FTS measurements were compared to surface measurements made by the AGAGE network and output from the SLIMCAT three-dimensional (3-D) chemical transport model, which is constrained by similar surface data. ACE-FTS measurements of CFCs show declining trends which agree with both AGAGE and SLIMCAT values. There are problems with the ACE-FTS retrievals of CFC-113 and HCFCs, with work currently ongoing to correct these problems. At lower altitudes the volume mixing ratio (VMR) of these species increase with altitude. This is due to problems with the retrievals at high beta angle (the angle between the orbital plane and the Earth-Sun vector). Although some of the retrievals have problems, we are confident that the trends are generally reliable. The concentrations of HCFCs appear to be increasing with ACE-FTS, SLIMCAT and AGAGE all showing positive trends. ACE-FTS measurements of the decomposition products (COFCl and COCl₂) do not show any significant trends. SLIMCAT data show a negative trend for COFCl which corresponds to the decrease in CFC-11, its assumed major source, during this time. COF₂ measurements from ACE-FTS show an increasing trend, while SLIMCAT shows a decreasing trend again linked to its assumed production from CFCs. ClONO₂ is highly photosensitive, thus the ACE-FTS occultations have been divided into local morning and evening occultations. Evening measurements of ClONO₂ show a decreasing trend in VMR, while morning measurements show an increasing trend. The reason for this difference is not understood at this time. The SLIMCAT output used in this study was not saved as local sunrise and sunset: therefore, only 24 h mean fields are available for ClONO₂. These SLIMCAT data show a decreasing trend. SLIMCAT and ACE-FTS both show an increasing trend in the VMR of HF and a decreasing trend in the VMR of HCl. These results illustrate the success of the Montreal Protocol in reducing ozone depleting substances. The reduction in anthropogenic chlorine emissions has led to a decrease in the VMR of stratospheric HCl. The replacement of CFCs with HCFCs has led to an increase in the VMR of HF in the stratosphere. As chlorine-containing compounds continue to be phased out and replaced by fluorine-containing molecules, it is likely that total atmospheric fluorine will continue increasing in the near future.