101 resultados para Photoacoustic spectrometer


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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.

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In part I of this study [Baggott, Clase, and Mills, Spectrochim. Acta Part A 42, 319 (1986)] we presented FTIR spectra of gas phase cyclobutene and modeled the v=1–3 stretching states of both olefinic and methylenic C–H bonds in terms of a local mode model. In this paper we present some improvements to our original model and make use of recently derived ‘‘x,K relations’’ to find the equivalent normal mode descriptions. The use of both the local mode and normal mode approaches to modeling the vibrational structure is described in some detail. We present evidence for Fermi resonance interactions between the methylenic C–H stretch overtones and ring C–C stretch vibrations, revealed in laser photoacoustic spectra in the v=4–6 region. An approximate model vibrational Hamiltonian is proposed to explain the observed structure and is used to calculate the dynamics of the C–H stretch local mode decay resulting from interaction with lower frequency ring modes. The implications of our experimental and theoretical studies for mode‐selective photochemistry are discussed briefly.

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Intracavity photoacoustic overtone spectrum of monofluoroacetylene, HCCF, has been recorded in the wave number region 10 750–14 500 cm−1 with a titanium:sapphire ring laser. The spectrum contains many dense vibration–rotation band systems which can be resolved with Doppler limited resolution. Altogether 58 individual overtone bands have been analyzed rotationally. Many of the observed bands show perturbations of which some have been attributed to anharmonic resonance interactions. A Fermi resonance model based on conventional rectilinear normal coordinate theory has been used to assign vibrationally bands from this work and from earlier studies. Many of the observed vibrational term values and rotational constants can be reproduced well with this model. The results show the importance of the Fermi resonance interactions at the high overtone excitations.

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We discuss a novel approach to the development of an ultrasonic optical force-feedback measurement microphone suitable for observing biophotonic related photoacoustic and photothermal phenomena at high modulation frequencies and spatial resolution.

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An H-infinity control strategy has been developed for the design of controllers used in feedback controlled electrical substitution measurements (FCESM). The methodology has the potential to provide substantial improvements in both response time and resolution of a millimetre-wave absolute photoacoustic power meter.

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The global behavior of the extratropical tropopause transition layer (ExTL) is investigated using O3, H2O, and CO measurements from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) on Canada’s SCISAT-1 satellite obtained between February 2004 and May 2007. The ExTL depth is derived using H2O-O3 and CO-O3 correlations. The ExTL top derived from H2O-O3 shows an increase from roughly 1–1.5 km above the thermal tropopause in the subtropics to 3–4 km (2.5–3.5 km) in the north (south) polar region, implying somewhat weaker tropospherestratosphere- transport in the Southern Hemisphere. The ExTL bottom extends ~1 km below the thermal tropopause, indicating a persistent stratospheric influence on the troposphere at all latitudes. The ExTL top derived from the CO-O3 correlation is lower, at 2 km or ~345 K (1.5 km or ~335 K) in the Northern (Southern) Hemisphere. Its annual mean coincides with the relative temperature maximum just above the thermal tropopause. The vertical CO gradient maximizes at the thermal tropopause, indicating a local minimum in mixing within the tropopause region. The seasonal changes in and the scales of the vertical H2O gradients show a similar pattern as the static stability structure of the tropopause inversion layer (TIL), which provides observational support for the hypothesis that H2O plays a radiative role in forcing and maintaining the structure of the TIL.

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A detailed spectrally-resolved extraterrestrial solar spectrum (ESS) is important for line-by-line radiative transfer modeling in the near-infrared (near-IR). Very few observationally-based high-resolution ESS are available in this spectral region. Consequently the theoretically-calculated ESS by Kurucz has been widely adopted. We present the CAVIAR (Continuum Absorption at Visible and Infrared Wavelengths and its Atmospheric Relevance) ESS which is derived using the Langley technique applied to calibrated observations using a ground-based high-resolution Fourier transform spectrometer (FTS) in atmospheric windows from 2000–10000 cm-1 (1–5 μm). There is good agreement between the strengths and positions of solar lines between the CAVIAR and the satellite-based ACE-FTS (Atmospheric Chemistry Experiment-FTS) ESS, in the spectral region where they overlap, and good agreement with other ground-based FTS measurements in two near-IR windows. However there are significant differences in the structure between the CAVIAR ESS and spectra from semi-empirical models. In addition, we found a difference of up to 8 % in the absolute (and hence the wavelength-integrated) irradiance between the CAVIAR ESS and that of Thuillier et al., which was based on measurements from the Atmospheric Laboratory for Applications and Science satellite and other sources. In many spectral regions, this difference is significant, as the coverage factor k = 2 (or 95 % confidence limit) uncertainties in the two sets of observations do not overlap. Since the total solar irradiance is relatively well constrained, if the CAVIAR ESS is correct, then this would indicate an integrated “loss” of solar irradiance of about 30 W m-2 in the near-IR that would have to be compensated by an increase at other wavelengths.

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We present the first comprehensive intercomparison of currently available satellite ozone climatologies in the upper troposphere/lower stratosphere (UTLS) (300–70 hPa) as part of the Stratosphere-troposphere Processes and their Role in Climate (SPARC) Data Initiative. The Tropospheric Emission Spectrometer (TES) instrument is the only nadir-viewing instrument in this initiative, as well as the only instrument with a focus on tropospheric composition. We apply the TES observational operator to ozone climatologies from the more highly vertically resolved limb-viewing instruments. This minimizes the impact of differences in vertical resolution among the instruments and allows identification of systematic differences in the large-scale structure and variability of UTLS ozone. We find that the climatologies from most of the limb-viewing instruments show positive differences (ranging from 5 to 75%) with respect to TES in the tropical UTLS, and comparison to a “zonal mean” ozonesonde climatology indicates that these differences likely represent a positive bias for p ≤ 100 hPa. In the extratropics, there is good agreement among the climatologies regarding the timing and magnitude of the ozone seasonal cycle (differences in the peak-to-peak amplitude of <15%) when the TES observational operator is applied, as well as very consistent midlatitude interannual variability. The discrepancies in ozone temporal variability are larger in the tropics, with differences between the data sets of up to 55% in the seasonal cycle amplitude. However, the differences among the climatologies are everywhere much smaller than the range produced by current chemistry-climate models, indicating that the multiple-instrument ensemble is useful for quantitatively evaluating these models.