Terahertz Frequency-Domain Spectroscopy of Low-Pressure Acetonitrile Gas by a Photomixing Terahertz Synthesizer Referenced to Dual Optical Frequency Combs

A terahertz (THz) frequency synthesizer based on photomixing of two near-infrared lasers with a sub-THz to THz frequency offset is a powerful tool for spectroscopy of polar gas molecules due to its broad spectral coverage; however, its frequency accuracy and resolution are relatively low. To tune the output frequency continuously and widely while maintaining its traceability to a frequency standard, we developed a photomixing THz synthesizer phase-locked to dual optical frequency combs (OFCs). While the phase-locking to dual OFCs ensured continuous tuning within a spectral range of 120 GHz, in addition to the traceability to the frequency standard, use of a broadband uni-traveling carrier photodiode for photomixing enabled the generation of CW-THz radiation within a frequency range from 0.2 to 1.5 THz. We demonstrated THz frequency-domain spectroscopy of gas-phase acetonitrile CH₃CN and its isotope CH₃ ¹³CN in the frequency range of 0.600–0.720 THz using this THz synthesizer. Their rotational transitions were assigned with a frequency accuracy of 8.42?×?10^?8 and a frequency resolution of 520 kHz. Furthermore, the concentration of the CH₃CN gas at 20 Pa was determined to be (5.41?±?0.05)?×?10¹⁴ molecules/cm³ by curve fitting analysis of the measured absorbance spectrum, and the mixture ratio of the mixed CH₃CN/CH₃ ¹³CN gas was determined to be 1:2.26 with a gas concentration of 10¹⁴–10¹⁵ molecules/cm³. The developed THz synthesizer is highly promising for high-precision THz-FDS of low-pressure molecular gases and will enable the qualitative and quantitative analyses of multiple gases.