Complete reactants-to-products observation of a gas-phase chemical reaction with broad, fast mid-infrared frequency combs

TL;DR

This paper introduces a high-speed, broadband mid-infrared dual frequency comb spectrometer capable of observing all reactants and products in a gas-phase chemical reaction, providing detailed, real-time insights into reaction dynamics.

Contribution

The authors develop a novel spectrometer that combines broadband coverage, high spectral resolution, and microsecond temporal resolution for comprehensive reaction monitoring.

Findings

Successfully quantified all species in a formaldehyde decomposition reaction.

Achieved microsecond tracking of fast chemical process dynamics.

Enhanced understanding of reaction pathways and rates.

Abstract

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 and fast, and existing diagnostic approaches provide incomplete information. For example, mass spectrometry is optimized to gather snapshots of the presence of many chemical species, while conventional laser spectroscopy can quantify a single chemical species through time. Here we optimize for multiple objectives by introducing a high-speed and broadband, mid-infrared dual frequency comb absorption spectrometer. The optical bandwidth of >1000 cm-1 covers absorption fingerprints of many species with spectral resolution <0.03 cm-1 to accurately discern their absolute quantities. Key to this advance are 1 GHz pulse repetition rate frequency combs covering the 3-5 um region that enable microsecond tracking 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 advances understanding of chemical reaction pathways and rates and opens the door for novel developments such as combining high-speed chemistry with machine learning.