Synchronized Two-Color Time-Resolved Dual-Comb Spectroscopy for Quantitative Detection of HOx Radicals Formed from Criegee Intermediates

Criegee intermediates, derived from ozonolysis of alkenes and recognized as key species in the production of nonphotolytic free radicals, play a crucial role in atmospheric chemistry. Here, we present a spectrometer based on synchronized two-color time-resolved dual-comb spectroscopy, enabling simultaneous spectral acquisitions in two molecular fingerprint regions near 2.9 and 7.8 μm. Upon flash photolysis of CH2I2/O2/N2 gas mixtures, multiple reaction species, involving the simplest Criegee intermediates (CH2OO), formaldehyde (CH2O), hydroxyl (OH) and hydroperoxy (HO2) radicals are simultaneously detected with microsecond time resolution. The concentration of each molecule can be determined based on high-resolution rovibrational absorption spectroscopy. With quantitative detection and simulation of temporal concentration profiles of the targeted molecules at various conditions, the underlying reaction mechanisms and pathways related to the formation of the HOx radicals, which can be generated from decomposition of initially energized and vibrationally excited Criegee intermediates, are explored. This approach capable of achieving multispectral measurements with simultaneously high spectral and temporal resolutions opens up the opportunities for quantification of transient intermediates and products, thus, enabling elucidation of complex reaction mechanisms.