Gas-Phase Characterization of Adipic Acid, 6‑Hydroxycaproic Acid, and Their Thermal Decomposition Products by Rotational Spectroscopy

We report the spectroscopic investigation of two bifunctional aliphatic carboxylic acids, namely, adipic acid and 6-hydroxycaproic acid, in the gas phase by combining high-resolution rotational spectroscopy and supersonic expansions. Their pure rotational spectra were successfully identified and characterized. However, due to the low thermal stability of these two chemicals, the measured rotational spectra were significantly congested with transitions corresponding to their decomposition products upon heating. We observed cyclopentanone and adipic anhydride in the spectrum of adipic acid and ε-caprolactone and its monohydrate in the spectrum of 6-hydroxycaproic acid. On the basis of the distinct fingerprints of both carboxylic acids and a series of their decomposition products, the spectra were analyzed in a time-segmented manner. This provides valuable insights into the thermal decomposition mechanisms of these two samples over time, which highlights the robustness of microwave spectroscopy as a potent tool for analyzing complex chemical mixtures in a species-, isomer-, and conformer-selective way.