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High-Resolution Absorption Studies of the Ã1A2−X̃1A1 202401 Band of Formaldehyde

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Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QZ, U.K.
* Corresponding author. E-mail: [email protected]. Phone: +44 (0)1865 285723. Fax: +44 (0)1865 275 410.
Cite this: J. Phys. Chem. A 2009, 113, 24, 6689–6696
Publication Date (Web):May 21, 2009
https://doi.org/10.1021/jp9023475
Copyright © 2009 American Chemical Society

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    Abstract

    Absolute peak absorption cross sections and pressure broadening coefficients have been recorded with sub-Doppler limited instrumental resolution for selected rotational lines in the 202401 vibronic band of the formaldehyde Ã1A2−X̃1A1 electronic transition. The measured absorption cross sections range between (0.18 ± 0.01) and (10.1 ± 0.08) × 10−19 cm2 molecule−1 and are considerably larger than values from the literature recorded using apparatus where instrumental broadening was significant. However, comparisons with spectral simulations with equivalent resolution from Smith et al. (J. Phys. Chem. A2006, 110, 11645−11653) are in excellent agreement. Pressure broadening was studied for the collision partners CH2O, CO2, N2, O2, Ne, Kr, Ar, and He, and the resulting broadening coefficients were found to be reduced in comparison to equivalent values measured in infrared regions, consistent with the reduced dipole moment of the upper state probed in this work. Cavity-enhanced absorption spectroscopy (CEAS) measurements were undertaken using calibrated low concentration (2.9−4.6 ppmv) samples from a permeation source and demonstrate a noise equivalent absorption of 1.2 × 10−6 cm−1 Hz−1/2. This implies a minimum detectable formaldehyde concentration with the current system in atmospheric air of 172 ppbv Hz−1/2.

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    Cited By

    This article is cited by 5 publications.

    1. Cheryl Tatum Ernest, Dieter Bauer, and Anthony J. Hynes . Radical Quantum Yields from Formaldehyde Photolysis in the 30 400–32 890 cm–1 (304–329 nm) Spectral Region: Detection of Radical Photoproducts Using Pulsed Laser Photolysis–Pulsed Laser Induced Fluorescence. The Journal of Physical Chemistry A 2012, 116 (26) , 6983-6995. https://doi.org/10.1021/jp2117399
    2. Cheryl Tatum Ernest, Dieter Bauer, and Anthony J. Hynes . High-Resolution Absorption Cross Sections of Formaldehyde in the 30285–32890 cm–1 (304–330 nm) Spectral Region. The Journal of Physical Chemistry A 2012, 116 (24) , 5910-5922. https://doi.org/10.1021/jp210008g
    3. L. Wang, T. R. Sharples. Intrapulse quantum cascade laser spectroscopy: pressure induced line broadening and shifting in the ν 6 band of formaldehyde. Applied Physics B 2012, 108 (2) , 427-435. https://doi.org/10.1007/s00340-012-5085-7
    4. Paul W. Seakins, Mark A. Blitz. Developments in Laboratory Studies of Gas-Phase Reactions for Atmospheric Chemistry with Applications to Isoprene Oxidation and Carbonyl Chemistry. Annual Review of Physical Chemistry 2011, 62 (1) , 351-373. https://doi.org/10.1146/annurev-physchem-032210-102538
    5. Marc N. Fiddler, Israel Begashaw, Matthew A. Mickens, Michael S. Collingwood, Zerihun Assefa, Solomon Bililign. Laser Spectroscopy for Atmospheric and Environmental Sensing. Sensors 2009, 9 (12) , 10447-10512. https://doi.org/10.3390/s91210447