Demonstration of a uniform, high-pressure, high-temperature gas cell with a dual frequency comb absorption spectrometer

Highlights: • Design of a highly uniform, long path length, optically accessible gas cell for laboratory absorption spectroscopy at high-pressure and -temperature conditions. • Complete characterization of the gas cell temperature uniformity up to 1000 K and 50 bar demonstrates that temperature deviations remain less than 4.5% across the 45.82 cm absorbing path length at all conditions. • Broadband, high resolution spectroscopy of the CO2 3v3band at pressures between 0.2 and 20 bar and temperatures up to 1000 K using a dual frequency comb absorption spectrometer. • Comparison to a HITRAN2016-based absorption model demonstrates the need to improve line shape parameters for high temperatures as well as evidence of non-Lorentzian effects (line mixing) in the high-pressure spectra. Accurate absorption models for gases at high pressure and temperature support advanced optical combustion diagnostics and aid in the study of harsh planetary atmospheres. Developing and validating absorption models for these applications requires recreating the extreme temperature and pressure conditions of these environments in static, uniform, well-known conditions in the laboratory. Here, we present the design of a new gas cell to enable reference-quality absorption spectroscopy at high pressure and temperature. The design centers on a carefully controlled quartz sample cell housed at the core of a pressurized ceramic furnace. The half-meter sample cell is relatively long compared to past high-pressure and -temperature absorption cells, and is surrounded by a molybdenum heat spreader that enables high temperature uniformity over the full length of the absorbing gas. We measure the temperature distribution of the sample gas using in situ thermocouples, and fully characterize the temperature uniformity across a full matrix of temperatures and pressures up to 1000 K and 50 bar. The results demonstrate that the new design enables highly uniform and precisely known temperature and pressure conditions across the full absorbing path length. Uniquely, we test the new gas cell with a broadband (~2500 cm⁻¹), high-resolution (0.0066 cm⁻¹) dual frequency comb spectrometer that enables highly resolved absorption spectroscopy across a wide range of temperature and pressure conditions. With this carefully characterized system, we measure the spectrum of CO₂ between 6800 and 7000 cm⁻¹ at pressures between 0.2 and 20 bar, and temperatures up to 1000 K. The measurements reveal discrepancies from spectra predicted by the HITRAN2016 database with a Voigt line shape at both low- and high-pressure conditions. These results motivate future work to expand absorption models and databases to accurately model high-pressure and -temperature spectra in combustion and planetary science research.