High-Resolution Absorption Cross Sections of Formaldehyde in the 30285–32890 cm<sup>–1</sup> (304–330 nm) Spectral Region

Ernest, C. Tatum; Bauer, Dieter; Hynes, Anthony J.

doi:10.1021/jp210008g

Cited by 10 publications

(12 citation statements)

References 45 publications

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“…Comparison of the high-resolution absolute cross section, σ HCHO , obtained previously (top panel) with the action spectrum, relative Φ H+HCO σ HCHO , obtained at the same resolution (bottom panel).…”

Section: Resultsmentioning

confidence: 97%

“…The composite action spectrum was placed on an absolute wavelength scale using the previously obtained wavelength calibrated high-resolution absorption cross section. The error in the wavelength calibration is ±0.096 cm –1 …”

Section: Resultsmentioning

confidence: 99%

“…This results in an instrumental resolution better than 0.09 cm –1 . The unmixed dye laser fundamental was directed through an etalon, and the resulting fringe pattern was used to correct for nonlinearities in wavelength that result from scanning the dye laser as discussed elsewhere …”

Section: Experimental Designmentioning

confidence: 99%

“…Numerous measurements of HCHO absorption cross sections have been made under a wide range of different experimental parameters including spectral range, resolution, temperature, pressure, and method of HCHO generation. − As a necessary first step in our laboratory investigations of HCHO photochemistry, we have measured room temperature absolute absorption cross sections obtained at an instrumental resolution better than 0.09 cm –1 measured under conditions of low partial pressure of HCHO (<0.3 Torr) across the same spectral range examined in this study (30 285–32 890 cm –1 ) …”

Section: Introductionmentioning

confidence: 99%

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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

2012

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The relative quantum yield for the production of radical products, H + HCO, from the UV photolysis of formaldehyde (HCHO) has been measured using a pulsed laser photolysis–pulsed laser induced fluorescence (PLP–PLIF) technique across the 30,400–32,890 cm(–1) (304–329 nm) spectral region of the Ã(1)A2–X̃(1)A1 electronic transition. The photolysis laser had a bandwidth of 0.09 cm(–1), which is slightly broader than the Doppler width of a rotational line of formaldehyde at 300 K (0.07 cm(–1)), and the yield spectrum shows detailed rotational structure. The H and HCO photofragments were monitored using LIF of the OH radical as a spectroscopic marker. The OH radicals were produced by rapid reaction of the H and HCO photofragments with NO2. This technique produced an “action” spectrum that at any photolysis wavelength is the product of the H + HCO radical quantum yield and HCHO absorption cross section at the photolysis wavelength and is a relative measurement. Using the HCHO absorption cross section previously obtained in this laboratory, the relative quantum yield was determined two different ways. One produced band specific yields, and the other produced yields averaged over each 100 cm(–1). Yields were normalized to a value of 0.69 at 31,750 cm(–1) based on the current recommendation of Sander et al. (Sander, S. P.; Abbatt, J.; Barker, J. R.; Burkholder, J. B.; Friedl, R. R.; Golden, D. M.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Moortgat, G. K.; et al. Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation No. 17; Jet Propulsion Laboratory: Pasadena, CA, USA, 2011). The resulting radical quantum yields agree well with previous experimental studies and the current JPL recommendation but show greater wavelength dependent structure. A significant decrease in the quantum yield was observed for the 5(0)(1) + 1(0)(1)4(0)(1) combination band centered at 31,125 cm(–1). This band has a low absorption cross section and has little impact on the calculated atmospheric photodissociation rate but is a further indication of the complexity of HCHO photodissociation dynamics.

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Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

Section: Experimental Designmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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

2012

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“…Rufus et al, 2003), formaldehyde (HCHO, e.g. Ernest et al, 2012) water (Rothman et al, 2013), and chlorine monoxide (ClO Barton et al, 1984), Neuroth et al (1991) found strong, discrete and narrow bromine monoxide (BrO) absorption lines in the UV. Using these much more detailed and specific spectral features of the trace gases could not only substantially increase the selectivity but also in many cases increase the sensitivity of DOAS measurements.…”

mentioning

confidence: 99%

Mobile and high spectral resolution Fabry Pérot interferometer spectrographs for atmospheric remote sensing

Kuhn

Bobrowski

Wagner

et al. 2021

Preprint

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Abstract. Grating spectrographs (GS) are presently widely in use for atmospheric trace gas remote sensing in the ultraviolet (UV) and visible spectral range (e.g. differential optical absorption spectroscopy, DOAS). For typical DOAS applications, GSs have a spectral resolution of about half a nm corresponding to a resolving power R (ratio of operating wavelength to spectral resolution) in the range of 1000. This is sufficient to quantify the vibro-electronic spectral structure of the absorption of many trace gases with good accuracy and further allows for mobile (i.e. compact and stable) instrumentation. However, a much higher resolving power (R ≈ 105, i.e. a spectral resolution of about the width of an individual rotational absorption line) would facilitate the measurement of further trace gases (e.g. OH radicals), significantly reduce cross interferences due to other absorption and scattering processes, and provide enhanced sensitivity. Despite of these major advantages, only very few atmospheric studies with high resolution GSs are reported, mostly because increasing the resolving power of a GS leads to largely reduced light throughput and mobility. However, for many environmental studies, light throughput and mobility of measurement equipment are central limiting factors, for instance when absorption spectroscopy is applied to quantify reactive trace gases in remote areas (e.g. volcanoes) or from air borne or space borne platforms. Since more than a century, Fabry Pérot interferometers (FPIs) have been successfully used for high resolution spectroscopy in many scientific fields where they are known for their superior light throughput. However, except for a few studies, FPIs received hardly any attention in atmospheric trace gas remote sensing, despite their advantages. We propose different high resolution FPI spectrograph implementations and compare their light throughput and mobility to GSs with the same resolving power. We find that nowadays mobile high resolution FPI spectrographs can have a more than two orders of magnitude higher light throughput than their immobile high resolution GS counterparts. Compared to moderate resolution GSs (as routinely used for DOAS), a FPI spectrograph reaches a 250 times higher spectral resolution while the signal to noise ratio (SNR) is reduced by only a factor of 10. With a first compact prototype of a high resolution FPI spectrograph (R ≈ 148000, < 8 litres, < 5 kg) we demonstrate that these expectations are realistic. Using mobile and high resolution FPI spectrographs could have a large impact on atmospheric near UV to near IR remote sensing. Applications include the enhancement of sensitivity and selectivity of absorption measurements of many atmospheric trace gases and their isotopes, the direct quantification of OH radicals in the troposphere, high resolution O2 measurements for radiative transfer and aerosol studies and solar induced chlorophyll fluorescence quantification using Fraunhofer lines.

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Ultraviolet intracavity laser absorption spectroscopy

Zamir,

Cohen,

Lerer

et al. 2023

Sensors and Actuators B: Chemical

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High-Resolution Absorption Cross Sections of Formaldehyde in the 30285–32890 cm^–1 (304–330 nm) Spectral Region

Cited by 10 publications

References 45 publications

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

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

Mobile and high spectral resolution Fabry Pérot interferometer spectrographs for atmospheric remote sensing

Ultraviolet intracavity laser absorption spectroscopy

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High-Resolution Absorption Cross Sections of Formaldehyde in the 30285–32890 cm–1 (304–330 nm) Spectral Region

Cited by 10 publications

References 45 publications

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

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

Mobile and high spectral resolution Fabry Pérot interferometer spectrographs for atmospheric remote sensing

Ultraviolet intracavity laser absorption spectroscopy

Contact Info

Product

Resources

About

High-Resolution Absorption Cross Sections of Formaldehyde in the 30285–32890 cm^–1 (304–330 nm) Spectral Region

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

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