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Protonated hydrochlorous acid (HOClH+) has been examined theoretically. Equilibrium geometries have been optimized and harmonic vibrational frequencies obtained for each of the parent and protonated structures at various levels of theory employing second-order Mo\ller–Plesset perturbation interaction theory (MP2), singles and doubles excitation configuration interaction theory (CISD), and coupled-cluster theory (CCSD). Our study has found that protonation of the oxygen of HOCl is favored over protonation at the chlorine site. Protonation of the oxygen leads to a pyramidal structure of Cs symmetry. There is a planar Cs structure which is the inversion transition state. The inversion barrier is 3.2 kcal mol-1. The proton affinity of hypochlorous acid, HOCl, is found to be 153.1 kcal mol-1 at 0 K. © 1995 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The structure of ClO2 has been calculated for the X 2A‘ ground state using unrestricted Hartree–Fock (UHF), unrestricted second-order Mo/ller–Plesset perturbation (UMP2), configuration interaction using single and double excitation (CISD), and quadratic configuration interaction (QCI) ab initio molecular orbital methods. Calculations using UMP2 and CISD wave functions predict a ClO bond length of 1.728±0.01 Å. The single-configuration based QCI in the singles and doubles space with perturbation inclusion of triple substitutions, denoted QCISD(T), yield a ClO bond length of 2.205 Å. The QCI results are consistent with results of Jensen who showed that the ClO bond length is 2.181 Å using annihilated self-consistent methods (AUMP2). The thermochemistry of ClO2 radical has been calculated using MP2 and QCI methods using an isodesmic scheme. Our scheme predicts the heat of formation for ClO2 at 0 K to be 24.6±2 kcal mol-1. [ABSTRACT FROM AUTHOR]

The Geostationary Fourier Transform Spectrometer (GeoFTS) is designed to measure high-resolution spectra of reflected sunlight in three near-infrared bands centered around 0.76, 1.6, and 2.3 µm and to deliver simultaneous retrievals of column-averaged dry air mole fractions of CO2, CH4, CO, and H2O (denoted XCO2, XCH4, XCO, and XH2O, respectively) at different times of day over North America. In this study, we perform radiative transfer simulations over both clear-sky and all-sky scenes expected to be observed by GeoFTS and estimate the prospective performance of retrievals based on results from Bayesian error analysis and characterization. We find that, for simulated clear-sky retrievals, the average retrieval biases and single-measurement precisions are < 0.2% for XCO2, XCH4, and XH2O, and < 2% for XCO, when the a priori values have a bias of 3%and an uncertainty of 3 %. In addition, an increase in the amount of aerosols and ice clouds leads to a notable increase in the retrieval biases and slight worsening of the retrieval precisions. Furthermore, retrieval precision is a strong function of signal-to-noise ratio and spectral resolution. This simulation study can help guide decisions on the design of the GeoFTS observing system, which can result in cost-effective measurement strategies while achieving satisfactory levels of retrieval precisions and biases. The simultaneous retrievals at different times of day will be important for more accurate estimation of carbon sources and sinks on fine spatiotemporal scales and for studies related to the atmospheric component of the water cycle. [ABSTRACT FROM AUTHOR]

Atmospheric absorption in the O2 A-band (12 950-13200 cm-1) offers a unique opportunity to retrieve aerosol extinction profiles from space-borne measurements due to the large dynamic range of optical thickness in that spectral region. Absorptions in strong O2 lines are saturated; therefore, any radiance measured in these lines originates from scattering in the upper part of the atmosphere. Outside of O2 lines, or in weak lines, the atmospheric column absorption is small, and light penetrates to lower atmospheric layers, allowing for the quantification of aerosols and other scatterers near the surface. While the principle of aerosol profile retrieval using O2 A-band absorption from space is well known, a thorough quantification of the information content, i.e., the amount of vertical profile information that can be obtained, and the dependence of the information content on the spectral resolution of the measurements, has not been thoroughly conducted. Here, we use the linearized vector radiative transfer model VLIDORT to perform spectrally resolved simulations of atmospheric radiation in the O2 A-band in the presence of aerosol for four different generic scenarios: Urban, Highly polluted, Elevated layer, and Marine-Arctic. The high-resolution radiances emerging from the top of the atmosphere are degraded to different spectral resolutions, simulating spectrometers with different resolving powers. We use optimal estimation theory to quantify the information content in the aerosol profile retrieval with respect to different aerosol parameters and instrument spectral resolutions. The simulations show that better spectral resolution generally leads to an increase in the total amount of information that can be retrieved, with the number of degrees of freedom (DoF) varying between 0.34-2.11 at low resolution (5 cm-1) to 3.43-5.92 at high resolution (0.05 cm-1) for the four different cases. A particularly strong improvement was found in the retrieval of tropospheric aerosol extinction profiles in the lowest 5km of the atmosphere. At high spectral resolutions (0.05 cm-1), 1.18-1.7 and 1.31-2.34 DoF can be obtained in the lower (0-2 km) and middle (2-5 km) troposphere, respectively, for the different cases. Consequently a separation of lower and mid tropospheric aerosols is possible, implying the feasibility of identification of elevated biomass burning aerosol plumes (Elevated layer scenario). We find that higher single scattering albedo (SSA) allows for the retrieval of more aerosol information. However, the dependence on SSA is weaker at higher spectral resolutions. The Marine (surface albedo 0.05) and Arctic (surface albedo 0.9) cases show that the dependence of DoF on the surface albedo decreases with higher resolution. While at low resolution (5 cm-1) the DoF is 1 for the Marine case and 0.34 for the Arctic case, the DoF considerably increase at 0.05 cm-1 resolution to 3.8 and 3.4, respectively. In the Arctic case this is an improvement of a factor of 10. The simulations also reveal a moderate dependence of information content on the integration time of the measurements, i.e., the noise of the spectra. However, our results indicate that a larger increase in DoF is obtained by an increase in spectral resolution despite lower signal-to-noise ratios. [ABSTRACT FROM AUTHOR]

The Los Angeles basin is a significant anthropogenic source of major greenhouse gases (CO2 and CH4) and the pollutant CO, contributing significantly to regional and global climate change. We present a novel approach for monitoring the spatial and temporal distributions of greenhouse gases in the Los Angeles basin using a highresolution spectroscopic remote sensing technique. A new Fourier Transform Spectrometer called CLARS-FTS has been deployed since May 2010 at JPL's California Laboratory for Atmospheric Remote Sensing (CLARS) on Mt. Wilson, California for automated long-term measurements of greenhouse gases. The instrument design and performance of CLARS-FTS are presented. From its mountaintop location at an altitude of 1673 m, the instrument points at a programmed sequence of ground target locations in the Los Angeles basin, recording spectra of reflected near-IR solar radiation. Column-averaged dry-air mole fractions of greenhouse gases (XGHG) including XCO2, XCH4, and XCO are retrieved several times per day for each target. Spectra from a local Spectralon® scattering plate are also recorded to determine background (free tropospheric) column abundances above the site. Comparisons between measurements from LA basin targets and the Spectralon® plate provide estimates of the boundary layer partial column abundances of the measured species. Algorithms are described for transforming the measured interferograms into spectra, and for deriving column abundances from the spectra along with estimates of the measurement precision and accuracy. The CLARS GHG measurements provide a means to infer relative, and possibly absolute, GHG emissions. [ABSTRACT FROM AUTHOR]

We have integrated observations of tropospheric ozone, very short-lived (VSL) halocarbons and reactive iodine and bromine species from a wide variety of tropical data sources with the global CAM-Chem chemistry-climate model and offline radiative transfer calculations to compute the contribution of halogen chemistry to ozone loss and associated radiative impact in the tropical marine troposphere. The inclusion of tropospheric halogen chemistry in CAM-Chem leads to an annually averaged depletion of around 10% (∼2.5 Dobson units) of the tropical tropospheric ozone column, with largest effects in the middle to upper troposphere. This depletion contributes approximately -0.10Wm-2 to the radiative flux at the tropical tropopause. This negative flux is of similar magnitude to the ∼0.33Wm-2 contribution of tropospheric ozone to presentday radiative balance as recently estimated from satellite observations. We find that the implementation of oceanic halogen sources and chemistry in climate models is an important component of the natural background ozone budget and we suggest that it needs to be considered when estimating both preindustrial ozone baseline levels and long term changes in tropospheric ozone. [ABSTRACT FROM AUTHOR]

We have integrated observations of tropospheric ozone, very short-lived (VSL) halocarbons and reactive iodine and bromine species from a wide variety of tropical data sources with the global CAM-Chem chemistry-climate model and offline radiative transfer calculations to compute the contribution of halogen chemistry to ozone loss and associated radiative impact in the tropical marine troposphere. The inclusion of tropospheric halogen chemistry in CAM-Chem leads to an annually averaged depletion of around 10% (~2.5 Dobson units) of the tropical tropospheric ozone column, with largest effects in the middle to upper troposphere. This depletion contributes approximately -0.10 W m-2 to the radiative flux at the tropical tropopause. This negative flux is of similar magnitude to the ~0.33 W m-2 contribution of tropospheric ozone to presentday radiative balance as recently estimated from satellite observations. We find that the implementation of oceanic halogen sources and chemistry in climate models is an important component of the natural background ozone budget and we suggest that it needs to be considered when estimating both preindustrial ozone baseline levels and long term changes in tropospheric ozone. [ABSTRACT FROM AUTHOR]

The structure and heat of formation for hydrochlorous acid (HOCl) has been examined using post-Hartree methods which include second-order Mo\ller–Plesset theory perturbation and quadratic configuration interaction theory. The heat formation of HOCl is theoretically estimated to be -19.9±1 kcal mol-1 and compared well with the experimental determinations. [ABSTRACT FROM AUTHOR]