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

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.