Extremely sensitive detection of NO<sub>2</sub> employing off-axis integrated cavity output spectroscopy coupled with multiple-line integrated absorption spectroscopy

Gottipaty N. Rao; Andreas Karpf

doi:10.1364/AO.50.001915

Applied Optics
Vol. 50,
Issue 13,
pp. 1915-1924
(2011)
•https://doi.org/10.1364/AO.50.001915

Extremely sensitive detection of ${NO}_{2}$ employing off-axis integrated cavity output spectroscopy coupled with multiple-line integrated absorption spectroscopy

Gottipaty N. Rao and Andreas Karpf

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Gottipaty N. Rao and Andreas Karpf, "Extremely sensitive detection of NO₂ employing off-axis integrated cavity output spectroscopy coupled with multiple-line integrated absorption spectroscopy," Appl. Opt. 50, 1915-1924 (2011)

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- Atmospheric and Oceanic Optics
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About this Article
History
- Original Manuscript: November 24, 2010
- Revised Manuscript: February 14, 2011
- Manuscript Accepted: February 16, 2011
- Published: April 28, 2011
Virtual Issues
Virtual Journal for Biomedical Optics Vol. 6, Iss. 6

Abstract

We report on the development of a new sensor for ${NO}_{2}$ with ultrahigh sensitivity of detection. This has been accomplished by combining off-axis integrated cavity output spectroscopy (OA-ICOS) (which can provide large path lengths of the order of several kilometers in a small volume cell) with multiple-line integrated absorption spectroscopy (MLIAS) (where we integrate the absorption spectra over a large number of rotational–vibrational transitions of the molecular species to further improve the sensitivity). Employing an external cavity quantum cascade laser operating in the $1601 - 1670 {cm}^{- 1}$ range and a high-finesse optical cavity, the absorption spectra of ${NO}_{2}$ over 100 transitions in the R band have been recorded. From the observed linear relationship between the integrated absorption versus concentration of ${NO}_{2}$ and the standard deviation of the integrated absorption signal, we report an effective sensitivity of detection of approximately $28 ppt$ (parts in $10^{12}$ ) for ${NO}_{2}$ . To the best of our knowledge, this is among the most sensitive levels of detection of ${NO}_{2}$ to date.

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Central Frequency of Doublet ( ${cm}^{- 1}$ )	Upper State $(\begin{matrix} ν_{1} & ν_{3} & ν_{3} \end{matrix}) - (\begin{matrix} N^{'} & K_{a}^{'} & K_{c}^{'} \end{matrix})$	Lower State $(\begin{matrix} ν_{1} & ν_{3} & ν_{3} \end{matrix}) - (\begin{matrix} N^{''} & K_{a}^{''} & K_{c}^{''} \end{matrix})$
1630.326	$(\begin{matrix} 0 & 0 & 1 \end{matrix}) - (\begin{matrix} 17 & 1 & 16 \end{matrix})$	$(\begin{matrix} 0 & 0 & 0 \end{matrix}) - (\begin{matrix} 16 & 1 & 15 \end{matrix})$
1630.328	$(\begin{matrix} 0 & 0 & 1 \end{matrix}) - (\begin{matrix} 17 & 0 & 17 \end{matrix})$	$(\begin{matrix} 0 & 0 & 0 \end{matrix}) - (\begin{matrix} 16 & 0 & 16 \end{matrix})$

Central Frequency of Doublet ( ${cm}^{- 1}$ )	Upper State $(\begin{matrix} ν_{1} & ν_{3} & ν_{3} \end{matrix}) - (\begin{matrix} N^{'} & K_{a}^{'} & K_{c}^{'} \end{matrix})$	Lower State $(\begin{matrix} ν_{1} & ν_{3} & ν_{3} \end{matrix}) - (\begin{matrix} N^{''} & K_{a}^{''} & K_{c}^{''} \end{matrix})$
1655.315	$(\begin{matrix} 0 & 0 & 1 \end{matrix}) - (\begin{matrix} 58 & 1 & 58 \end{matrix})$	$(\begin{matrix} 0 & 0 & 0 \end{matrix}) - (\begin{matrix} 57 & 1 & 57 \end{matrix})$
1655.456	$(\begin{matrix} 0 & 0 & 1 \end{matrix}) - (\begin{matrix} 57 & 1 & 56 \end{matrix})$	$(\begin{matrix} 0 & 0 & 0 \end{matrix}) - (\begin{matrix} 56 & 1 & 55 \end{matrix})$
1655.563	$(\begin{matrix} 0 & 0 & 1 \end{matrix}) - (\begin{matrix} 57 & 2 & 55 \end{matrix})$	$(\begin{matrix} 0 & 0 & 0 \end{matrix}) - (\begin{matrix} 56 & 2 & 54 \end{matrix})$
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1656.410	$(\begin{matrix} 0 & 0 & 1 \end{matrix}) - (\begin{matrix} 59 & 1 & 58 \end{matrix})$	$(\begin{matrix} 0 & 0 & 0 \end{matrix}) - (\begin{matrix} 58 & 1 & 57 \end{matrix})$
1656.596	$(\begin{matrix} 0 & 0 & 1 \end{matrix}) - (\begin{matrix} 59 & 2 & 57 \end{matrix})$	$(\begin{matrix} 0 & 0 & 0 \end{matrix}) - (\begin{matrix} 58 & 2 & 56 \end{matrix})$

Central Frequency of Doublet ( ${cm}^{- 1}$ )	Upper State $(\begin{matrix} ν_{1} & ν_{3} & ν_{3} \end{matrix}) - (\begin{matrix} N^{'} & K_{a}^{'} & K_{c}^{'} \end{matrix})$	Lower State $(\begin{matrix} ν_{1} & ν_{3} & ν_{3} \end{matrix}) - (\begin{matrix} N^{''} & K_{a}^{''} & K_{c}^{''} \end{matrix})$
1630.326	$(\begin{matrix} 0 & 0 & 1 \end{matrix}) - (\begin{matrix} 17 & 1 & 16 \end{matrix})$	$(\begin{matrix} 0 & 0 & 0 \end{matrix}) - (\begin{matrix} 16 & 1 & 15 \end{matrix})$
1630.328	$(\begin{matrix} 0 & 0 & 1 \end{matrix}) - (\begin{matrix} 17 & 0 & 17 \end{matrix})$	$(\begin{matrix} 0 & 0 & 0 \end{matrix}) - (\begin{matrix} 16 & 0 & 16 \end{matrix})$

Central Frequency of Doublet ( ${cm}^{- 1}$ )	Upper State $(\begin{matrix} ν_{1} & ν_{3} & ν_{3} \end{matrix}) - (\begin{matrix} N^{'} & K_{a}^{'} & K_{c}^{'} \end{matrix})$	Lower State $(\begin{matrix} ν_{1} & ν_{3} & ν_{3} \end{matrix}) - (\begin{matrix} N^{''} & K_{a}^{''} & K_{c}^{''} \end{matrix})$
1655.315	$(\begin{matrix} 0 & 0 & 1 \end{matrix}) - (\begin{matrix} 58 & 1 & 58 \end{matrix})$	$(\begin{matrix} 0 & 0 & 0 \end{matrix}) - (\begin{matrix} 57 & 1 & 57 \end{matrix})$
1655.456	$(\begin{matrix} 0 & 0 & 1 \end{matrix}) - (\begin{matrix} 57 & 1 & 56 \end{matrix})$	$(\begin{matrix} 0 & 0 & 0 \end{matrix}) - (\begin{matrix} 56 & 1 & 55 \end{matrix})$
1655.563	$(\begin{matrix} 0 & 0 & 1 \end{matrix}) - (\begin{matrix} 57 & 2 & 55 \end{matrix})$	$(\begin{matrix} 0 & 0 & 0 \end{matrix}) - (\begin{matrix} 56 & 2 & 54 \end{matrix})$
1655.894	$(\begin{matrix} 0 & 0 & 1 \end{matrix}) - (\begin{matrix} 59 & 0 & 59 \end{matrix})$	$(\begin{matrix} 0 & 0 & 0 \end{matrix}) - (\begin{matrix} 58 & 0 & 58 \end{matrix})$
1656.301	$(\begin{matrix} 0 & 0 & 1 \end{matrix}) - (\begin{matrix} 60 & 1 & 60 \end{matrix})$	$(\begin{matrix} 0 & 0 & 0 \end{matrix}) - (\begin{matrix} 59 & 1 & 59 \end{matrix})$
1656.410	$(\begin{matrix} 0 & 0 & 1 \end{matrix}) - (\begin{matrix} 59 & 1 & 58 \end{matrix})$	$(\begin{matrix} 0 & 0 & 0 \end{matrix}) - (\begin{matrix} 58 & 1 & 57 \end{matrix})$
1656.596	$(\begin{matrix} 0 & 0 & 1 \end{matrix}) - (\begin{matrix} 59 & 2 & 57 \end{matrix})$	$(\begin{matrix} 0 & 0 & 0 \end{matrix}) - (\begin{matrix} 58 & 2 & 56 \end{matrix})$

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Applied Optics