High-accuracy and wide dynamic range frequency-based dispersion spectroscopy in an optical cavity

A spectroscopic method free from systematic errors is desired for many challenging applications of gas detection. Although existing cavity-enhanced techniques exhibit very high precision, their accuracy strongly depends on propagation of the light amplitude through an optical system and its detection. Here, we demonstrate that the frequency-based molecular dispersion spectroscopy, involving sub-Hz-level precision in frequency measurements of optical cavity resonances, leads to sub-per-mille accuracy and a wide dynamic range, both previously unattainable by any other spectroscopic technique. The method offers great sensitivity of 5×10^-11 cm^-1, high speed, limited only by the fundamental response time of the cavity, and traceability of both axes of the spectrum to the primary frequency standard. All these features are necessary for convenient realization of comprehensive molecular spectroscopy from Doppler up to collisional regime without changing the spectroscopic method and modification of the experimental setup. Moreover, the presented approach does not require linear, high-bandwidth nor phase-sensitive detectors and can be directly implemented in existing cavity-enhanced spectrometers utilizing either continuous-wave or coherent broadband radiation. We experimentally prove the predominance of frequency-based spectroscopy over intensity-based one. Our results motivate replacement of intensity-based absorption spectroscopy with a pure frequency-based dispersion one in applications where the highest accuracy is required.