AI Article Synopsis

  • Researchers measured the absolute line strengths of transitions in the ν1 fundamental band of hydroxyl radicals (OH) using laser photolysis of hydrogen peroxide (H2O2).
  • They utilized a synchronized two-color dual-comb spectrometer to capture high-resolution, time-resolved absorption spectra of both H2O2 and OH at different wavelengths.
  • The study also determined a pressure-independent rate coefficient for the reaction between OH and H2O2, achieving uncertainty in the OH line strengths below 10%, showcasing the potential of dual-comb spectroscopy for studying transient free radicals and their reactions.

Article Abstract

Absolute line strengths of several transitions in the ν1 fundamental band of the hydroxyl radical (OH) have been measured by simultaneous determination of hydrogen peroxide (H2O2) and OH upon laser photolysis of H2O2. Based on the well-known quantum yield for the generation of OH radicals in the 248-nm photolysis of H2O2, the line strength of the OH radicals can be accurately derived by adopting the line strength of the well-characterized transitions of H2O2 and analyzing the difference absorbance time traces of H2O2 and OH obtained upon laser photolysis. Employing a synchronized two-color dual-comb spectrometer, we measured high-resolution time-resolved absorption spectra of H2O2 near 7.9 µm and the OH radical near 2.9 µm, simultaneously, under varied conditions. In addition to the studies of the line strengths of the selected H2O2 and OH transitions, the kinetics of the reaction between OH and H2O2 were investigated. A pressure-independent rate coefficient kOH+H2O2 was determined to be [1.97 (+0.10/-0.15)] × 10-12 cm3 molecule-1 s-1 at 296 K and compared with other experimental results. By carefully analyzing both high-resolution spectra and temporal absorbance profiles of H2O2 and OH, the uncertainty of the obtained OH line strengths can be achieved down to <10% in this work. Moreover, the proposed two-color time-resolved dual-comb spectroscopy provides a new approach for directly determining the line strengths of transient free radicals and holds promise for investigations on their self-reaction kinetics as well as radical-radical reactions.

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http://dx.doi.org/10.1063/5.0176311DOI Listing

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