Absorption Cross-Sections of the C–H Overtone of Volatile Organic Compounds: 2 Methyl-1,3-Butadiene (Isoprene), 1,3-Butadiene, and 2,3-Dimethyl-1,3-Butadiene

Author： Cias Pawel Wang Chuji Dibble Theodore S.

Publisher： Society for Applied Spectroscopy

ISSN： 0003-7028

Source： Applied Spectroscopy, Vol.61, Iss.2, 2007-02, pp. : 230-236

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Abstract

Many molecules or transient radicals have well-documented absorption cross-sections in the ultraviolet (UV) region, but their absorption cross-sections in the near-infrared (NIR) region are much less often known and are difficult to measure. We propose a method to determine the unknown NIR absorption cross-sections using the known absorption cross-sections in the UV region, in which single-path UV absorption spectroscopy and NIR continuous wave cavity ringdown spectroscopy (cw-CRDS) are employed in a cross-arm reaction chamber for simultaneous measurements. Without knowing the actual sample partial pressures (or concentrations), the NIR absorption cross-sections can be accurately determined through the two sets of measurements. The method is demonstrated by measuring the NIR absorption cross-section of the first overtone of the asymmetric C–H stretch of 2-methyl-1,3-butadiene (isoprene) (3.24 (±0.16) × 10⁻²² cm² molecule⁻¹) at 1651.52 nm using the known value of the absorption cross-section at 220 nm. The diode laser wavelength was calibrated by atmospheric cavity ringdown spectra of CH₄, CO₂, and H₂O. By comparison with sample pressure measurements, this method can also be used as a pressure calibration means for the reaction chamber, and this has been demonstrated with two additional measurements of the absorption cross-sections of 1,3-butadiene and 2,3-dimethyl-1,3-butadiene (2.50 (± 0.08) × 10⁻²² and 2.82 (±0.16) × 10⁻²² cm² molecule⁻¹, respectively) at 1651.52 nm. The applicability of the method to determining absorption cross-sections using the simultaneous measurements of cw-CRDS and single-path absorption spectroscopy is discussed.