Infrared intensities of furan, pyrrole and thiophene: beyond the double harmonic approximation

Infrared intensities of the fundamental, overtone and combination transitions in furan, pyrrole and thiophene have been calculated using the variational normal coordinate code MULTIMODE. We use pure vibrational wavefunctions, and quartic force fields and cubic dipole moment vector surfaces, generated by density functional theory. The results are compared graphically with second-order perturbation calculations and with relative intensities from experiment for furan and pyrrole.

Assessment of the consistency of near-infrared water vapor line intensities using high-spectral-resolution ground-based Fourier transform measurements of solar radiation

Calculations of the absorption of solar radiation by atmospheric gases, and water vapor in particular, are dependent on the quality of databases of spectral line parameters. There has been increasing scrutiny of databases such as HITRAN in recent years, but this has mostly been performed on a band-by-band basis. We report nine high-spectral-resolution (0.03 cm(-1)) measurements of the solar radiation reaching the surface in southern England over the wave number range 2000 to 12,500 cm(-1) (0.8 to 5 mm) that allow a unique assessment of the consistency of the spectral line databases over this entire spectral region. The data are assessed in terms of the modeled water vapor column that is required to bring calculations and observations into agreement; for an entirely consistent database, this water vapor column should be constant with frequency. For the HITRAN01 database, the spread in water vapor column is about 11%, with distinct shifts between different spectral regions. The HITRAN04 database is in significantly better agreement (about 5% spread) in the completely updated 3000 to 8000 cm(-1) spectral region, but inconsistencies between individual spectral regions remain: for example, in the 8000 to 9500 cm(-1) spectral region, the results indicate an 18% (+/- 1%) underestimate in line intensities with respect to the 3000 to 8000 cm(-1) region. These measurements also indicate the impact of isotopic fractionation of water vapor in the 2500 to 2900 cm(-1) range, where HDO lines dominate over the lines of the most abundant isotope of H2O.

Intensities in infrared bands V: Bond polar properties in dimethylacetylene

The absolute intensities of all except one of the infra-red fundamental vibration bands of dimethyl acetylene have been determined, and the results have been used to compute polar properties of the C—H and C—C bonds. It has been found that if the very probable assumption is made that the acetylenic carbon atoms carry a residual negative charge, the hydrogen atoms in the C—H bonds must carry a residual positive charge. The probable value of the C—H dipole is about 04 Debye, and that of the C—C bond about 1 Debye. Comparisons have been made with the results of similar work with related molecules.

Assessment of the consistency of H2O line intensities over the near-infrared using sun-pointing ground-based Fourier transform spectroscopy

We report on the consistency of water vapour line intensities in selected spectral regions between 800–12,000 cm−1 under atmospheric conditions using sun-pointing Fourier transform infrared spectroscopy. Measurements were made across a number of days at both a low and high altitude field site, sampling a relatively moist and relatively dry atmosphere. Our data suggests that across most of the 800–12,000 cm−1 spectral region water vapour line intensities in recent spectral line databases are generally consistent with what was observed. However, we find that HITRAN-2008 water vapour line intensities are systematically lower by up to 20% in the 8000–9200 cm−1 spectral interval relative to other spectral regions. This discrepancy is essentially removed when two new linelists (UCL08, a compilation of linelists and ab-initio calculations, and one based on recent laboratory measurements by Oudot et al. (2010) [10] in the 8000–9200 cm−1 spectral region) are used. This strongly suggests that the H2O line strengths in the HITRAN-2008 database are indeed underestimated in this spectral region and in need of revision. The calculated global-mean clear-sky absorption of solar radiation is increased by about 0.3 W m−2 when using either the UCL08 or Oudot line parameters in the 8000–9200 cm−1 region, instead of HITRAN-2008. We also found that the effect of isotopic fractionation of HDO is evident in the 2500–2900 cm−1 region in the observations.

Intensities in the v7, v8 and v9 bands of CH2NH, and the harmonic force field of methyleneimine

A high resolution Fourier transform infrared spectrum of methyleneimine, HN=CH2, has been obtained in the gas phase in the region 700 to 1300 cm−1. The rovibrational line intensities of the three lowest fundamentals ν7 (A′), ν8 (A″), and ν9 (A″) have been simulated including all Coriolis interactions between the three bands, and by fitting the observed spectrum the relative signs and magnitudes of the vibrational transition moments have been determined. All of the available spectroscopic data have been used to determine the harmonic force field of methyleneimine.

Theoretical calculation of absorption intensities of C2H and C2D

The theory of dipole-allowed absorption intensities in triatomic molecules is presented for systems with three close-lying electronic states of doublet multiplicity. Its derivation is within the framework of a recently developed variational method [CARTER, S., HANDY, N. C., PUZZARINI, C., TARRONI, R., and PALMIERI, P., 2000, Molec. Phys., 98,1967]. The method has been applied to the calculation of the infrared absorption spectrum of the C2H radical and its deuterated isotopomer for energies up to 10000 cm(-1) above the ground state, using highly accurate ab initio diabatic potential energy and dipole moment surfaces. The calculated spectra agree very well with those recorded experimentally in a neon matrix [FORNEY, D., JACOX, M. E., and THOMPSON, W. E., 1995, J. molee. Spectrosc., 170, 178] and assignments in the high energy region of the IR spectra are proposed for the first time.

Ab initio prediction of the infrared-absorption spectrum of the C2Cl radical

The three lowest (1(2)A('), 2(2)A('), and 1(2)A(')) potential-energy surfaces of the C2Cl radical, correlating at linear geometries with (2)Sigma(+) and (2)Pi states, have been studied ab initio using a large basis set and multireference configuration-interaction techniques. The electronic ground state is confirmed to be bent with a very low barrier to linearity, due to the strong nonadiabatic electronic interactions taking place in this system. The rovibronic energy levels of the (CCCl)-C-12-C-12-Cl-35 isotopomer and the absolute absorption intensities at a temperature of 5 K have been calculated, to an upper limit of 2000 cm(-1), using diabatic potential-energy and dipole moment surfaces and a recently developed variational method. The resulting vibronic states arise from a strong mixture of all the three electronic components and their assignments are intrinsically ambiguous. (c) 2005 American Institute of Physics.

Ab initio prediction of the infrared absorption spectrum of the C2Br radical

The first three electronic states (1(2)A', 2(2)A', 1(2)A '') of the C2Br radical, correlating at linear geometries with (2)Sigma(+) and (2)Pi states, have been studied ab initio, using Multi Reference Configuration Interaction techniques. The electronic ground state is found to have a bent equilibrium geometry, R-CC = 1.2621 angstrom, R-CBr = 1.7967 angstrom, < CCBr 156.1 degrees, with a very low barrier to linearity. Similarly to the valence isoelectronic radicals C2F and C2Cl, this anomalous behaviour is attributed to a strong three-state non-adiabatic electronic interaction. The Sigma, Pi(1/2), Pi(3/2) vibronic energy levels and their absolute infrared absorption intensities at a temperature of 5K have been calculated for the (CCBr)-C-12-C-12-Br-79 isotopomer, to an upper limit of 2000 cm(-1), using ab initio diabatic potential energy and dipole moment surfaces and a recently developed variational method.

An improved algorithm for generating global window brightness temperatures from multiple satellite infrared imagery

An improved algorithm for the generation of gridded window brightness temperatures is presented. The primary data source is the International Satellite Cloud Climatology Project, level B3 data, covering the period from July 1983 to the present. The algorithm rakes window brightness, temperatures from multiple satellites, both geostationary and polar orbiting, which have already been navigated and normalized radiometrically to the National Oceanic and Atmospheric Administration's Advanced Very High Resolution Radiometer, and generates 3-hourly global images on a 0.5 degrees by 0.5 degrees latitude-longitude grid. The gridding uses a hierarchical scheme based on spherical kernel estimators. As part of the gridding procedure, the geostationary data are corrected for limb effects using a simple empirical correction to the radiances, from which the corrected temperatures are computed. This is in addition to the application of satellite zenith angle weighting to downweight limb pixels in preference to nearer-nadir pixels. The polar orbiter data are windowed on the target time with temporal weighting to account for the noncontemporaneous nature of the data. Large regions of missing data are interpolated from adjacent processed images using a form of motion compensated interpolation based on the estimation of motion vectors using an hierarchical block matching scheme. Examples are shown of the various stages in the process. Also shown are examples of the usefulness of this type of data in GCM validation.

Cooled Infrared Dichroic Beamsplitters and Filters for the MIRI Spectrometer and Imager (5-29µm)

The spectral design and fabrication of cooled (7K) mid-infrared dichroic beamsplitters and bandpass filter coatings for the MIRI spectrometer and imager are described. Design methods to achieve the spectral performance and coating materials are discussed.

Mid-infrared filters for astronomical and remote sensing instrumentation

As improvements to the optical design of spectrometer and radiometer instruments evolve with advances in detector sensitivity, use of focal plane detector arrays and innovations in adaptive optics for large high altitude telescopes, interest in mid-infrared astronomy and remote sensing applications have been areas of progressive research in recent years. This research has promoted a number of developments in infrared coating performance, particularly by placing increased demands on the spectral imaging requirements of filters to precisely isolate radiation between discrete wavebands and improve photometric accuracy. The spectral design and construction of multilayer filters to accommodate these developments has subsequently been an area of challenging thin-film research, to achieve high spectral positioning accuracy, environmental durability and aging stability at cryogenic temperatures, whilst maximizing the far-infrared performance. In this paper we examine the design and fabrication of interference filters in instruments that utilize the mid-infrared N-band (6-15 µm) and Q-band (16-28 µm) atmospheric windows, together with a rationale for the selection of materials, deposition process, spectral measurements and assessment of environmental durability performance.

Resolution of the uncertainties in the radiative forcing of HFC-134a

HFC-134a (CF3CH2F) is the most rapidly growing hydrofluorocarbon in terms of atmospheric abundance. It is currently used in a large number of household refrigerators and air-conditioning systems and its concentration in the atmosphere is forecast to increase substantially over the next 50–100 years. Previous estimates of its radiative forcing per unit concentration have differed significantly 25%. This paper uses a two-step approach to resolve this discrepancy. In the first step six independent absorption cross section datasets are analysed. We find that, for the integrated cross section in the spectral bands that contribute most to the radiative forcing, the differences between the various datasets are typically smaller than 5% and that the dependence on pressure and temperature is not significant. A “recommended'' HFC-134a infrared absorption spectrum was obtained based on the average band intensities of the strongest bands. In the second step, the “recommended'' HFC-134a spectrum was used in six different radiative transfer models to calculate the HFC-134a radiative forcing efficiency. The clear-sky instantaneous radiative forcing, using a single global and annual mean profile, differed by 8%, between the 6 models, and the latitudinally-resolved adjusted cloudy sky radiative forcing estimates differed by a similar amount.