Simultaneous determination of transient free radicals and reaction kinetics by high-resolution time-resolved dual-comb spectroscopy.

Quantitative determination of multiple transient species is critical in investigating reaction mechanisms and kinetics under various conditions. Dual-comb spectroscopy, a comb-laser-based multi-heterodyne interferometric technique that enables simultaneous achievement of broadband, high-resolution, and rapid spectral acquisition, opens a new era of time-resolved spectroscopic measurements. Employing an electro-optic dual-comb spectrometer with central wavelength near 3 µm coupled with a Herriott multipass absorption cell, here we demonstrate simultaneous determination of multiple species, including methanol, formaldehyde, HO and OH radicals, and investigate the reaction kinetics. In addition to quantitative spectral analyses of high-resolution and tens of microsecond time-resolved spectra recorded upon flash photolysis of precursor mixtures, we determine a rate coefficient of the HO + NO reaction by directly detecting both HO and OH radicals. Our approach exhibits potential in discovering reactive intermediates and exploring complex reaction mechanisms, especially those of radical-radical reactions.