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Molecular diagnostics are a primary tool of modern chemistry, enabling researchers to map chemical reaction pathways and rates to better design and control chemical systems. Many chemical reactions are complex, involving multiple species and reaction pathways occurring on µs or shorter timescales. Existing diagnostic approaches provide a subset of chemical and thermodynamic information. Here we optimize across many diagnostic objectives by introducing a high-speed and broadband, mid-infrared dual-frequency-comb absorption spectrometer. The optical bandwidth of >1000cm⁻¹covers absorption fingerprints of many species with spectral resolution <0.03cm⁻¹to accurately discern their absolute quantities. Key to this advance are 1 GHz pulse repetition rate mode-locked frequency combs covering the 3–5 µm region that enable a spectral acquisition rate of 290cm⁻¹per 17.5 µs per detector forin situtracking of fast chemical process dynamics. We demonstrate this system to quantify the abundances and temperatures of each species in the complete reactants-to-products breakdown of 1,3,5-trioxane, which exhibits a formaldehyde decomposition pathway that is critical to modern low-temperature combustion systems. By maximizing the number of observed species and improving the accuracy of temperature and concentration measurements, this spectrometer provides a pathway for modern chemistry approaches such as combining chemical models with machine learning to constrain or predict complex reaction mechanisms and rates. 

There are two established methods for measuring rotational Doppler shift: (1) heterodyne and (2) fringe. We identify a key distinction, that only the heterodyne method is sensitive to the rotating object’s phase, which results in significant differences in the signal-to-noise ratio (SNR) when measuring multiple rotating particles. When used to measure randomly distributed rotating particles, the fringe method produces its strongest SNR when a single particle is present and its SNR tends to zero as the number of particles increases, whereas the heterodyne method’s SNR increases proportionally to the number of particles in the beam.