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A sensitive high-resolution sub-Doppler detecting spectrometer, based on noise-immune cavity-enhanced optical heterodyne molecular spectrometry (NICE-OHMS), for trace gas detection of species whose transitions have severe spectral overlap with abundant concomitant species is presented. It is designed around a NICE-OHMS instrumentation utilizing balanced detection that provides shot-noise limited Doppler-broadened (Db) detection. By synchronous dithering the positions of the two cavity mirrors, the effect of residual etalons between the cavity and other surfaces in the system could be reduced. An Allan deviation of the absorption coefficient of 2.2 × 10^-13 cm^-1 at 60 s, which, for the targeted transition in C₂H₂, corresponds to a 3σ detection sensitivity of 130 ppt, is demonstrated. It is shown that despite significant spectral interference from CO₂ at the targeted transition, which precludes Db detection of C₂H₂, acetylene could be detected in exhaled breath of healthy smokers.

Accurate parameters of molecular transitions are needed for data analysis in many applications, ranging from atmospheric research to astrophysics and determination of fundamental constants. Optical frequency comb Fourier transform spectroscopy (OFC-FTS) is particularly well-suited for high-precision measurements of broadband molecular spectra. From these spectra, the parameters of individual transitions - all measured simultaneously under the same experimental conditions - can be determined. We use a mechanical OFC-FTS spectrometer with sub-nominal resolution [1, 2] to perform precise broadband measurements of entire molecular bands of CO2 using either direct absorption spectroscopy or cavity-enhanced complex refractive index spectroscopy (CE-CRIS) [3] and we extract line parameters for line shapes beyond the Voigt profile.

We present broadband cavity-enhanced complex refractive index spectroscopy (CE-CRIS), a technique for calibration-free determination of the complex refractive index of entire molecular bands via direct measurement of transmission modes of a Fabry-Perot cavity filled with the sample. The measurement of the cavity transmission spectrum is done using an optical frequency comb and a mechanical Fourier transform spectrometer with sub-nominal resolution. Molecular absorption and dispersion spectra (corresponding to the imaginary and real parts of the refractive index) are obtained from the cavity mode broadening and shift retrieved from fits of Lorentzian profiles to the individual cavity modes. This method is calibration-free because the mode broadening and shift are independent of the cavity parameters such as the length and mirror reflectivity. In this first demonstration of broadband CE-CRIS we measure simultaneously the absorption and dispersion spectra of three combination bands of CO2 in the range between 1525 nm and 1620 nm and achieve good agreement with theoretical models. This opens up for precision spectroscopy of the complex refractive index of several molecular bands simultaneously. 

We retrieve high precision absorption and dispersion spectra of the 3v(1)+v(3) band of CO2 from direct measurement of cavity transmission modes using an optical frequency comb and a mechanical Fourier transfolin spectrometer with sub-nominal resolution.

We demonstrate broadband calibration-free complex refractive index spectroscopy of entire molecular bands by direct measurement of transmission modes of a Fabry-Perot cavity using frequency comb-based Fourier transform spectrometer with sub-nominal resolution.

A model presented in an accompanying work predicts that mid-IR absorption signals from methane in trace concentrations in various buffer gases detected at pressures in the 1-100Torr range can be reduced and distorted due to depletion of the vibrational ground state if the molecules are exposed to laser powers in the tens of mW range or above. This work provides experimental evidence of such depletion in a resonant cavity under a variety of conditions, e.g. for intracavity laser powers up to 2W and for buffer gases of N-2 or dry air, and verifies the applicability of the model. It was found that the degree of depletion is significantly larger in N-2 than dry air, and that it increases with pressure for pressures up to around 10Torr (attributed to a decreased diffusion rate) but decreases with pressure for pressures above 20Torr (caused by an increased collisional vibrational decay rate). The maximum degree of depletion (similar to 80%) was obtained for methane in N-2 at around 15Torr. This implies that absorption spectrometry of methane can experience significant non-linear dependencies on laser power, pressure, as well as buffer gas composition. It is shown that depletion takes place also in (CH4)-C-13, which verifies the applicability of the model also for this isotopologue, and that NICE-OHMS signals detected in absorption phase are less affected by depletion than in dispersion. It was concluded that the absorption mode of detection can provide concentration assessments that are virtually free of influence of depletion for intracavity powers below 0.8 W. 

Shot-noise-limited Doppler-broadened (Db) noise-immune cavity-enhanced optical heterodyne molecular spectrometry (NICE-OHMS) has been realized by implementation of balanced detection. A characterization of the system based on Allan-Werle plots of the absorption coefficient, retrieved by fitting a model function to data, shows that the system has a white noise equivalent absorption per unit length per square root of bandwidth of 2.3 x 10(-13) cm(-1) Hz(-1/2), solely 44% above the shot noise limit, and a detection sensitivity of 2.2 x 10(-14) cm(-1) over 200 s, both being unprecedented for Db NICE-OHMS. The white noise response follows the expected inverse square root dependence on power that is representative of a shot-noise-limited response, which confirms that the system is shot-noise-limited. 

The detection sensitivity of noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) is often limited by background signals that bring in drifts. A novel realization of NICE-OHMS, termed differential NICE-OHMS, that both reduces such drifts and enlarges the molecular signal is presented. It is based on simultaneous detection of NICE-OHMS signals in reflection and transmission, followed by a subtraction of the former (properly weighted) from the latter. An Allan plot analysis shows that the instrumentation could demonstrate a noise equivalent absorption per unit length (NEAL) of 4.7 × 10⁻¹⁴ cm⁻¹, obtained for an integration time of 170 s.

Optical cavities provide high sensitivity to dispersion since their resonance frequencies depend on the index of refraction. We present a direct, broadband, and accurate measurement of the modes of a high finesse cavity using an optical frequency comb and a mechanical Fourier transform spectrometer with a kHz-level resolution. We characterize 16000 longitudinal cavity modes spanning 16 THz of bandwidth in terms of center frequency, linewidth, and amplitude. Using the center frequencies we retrieve the group delay dispersion of the cavity mirror coatings and pure N₂ with 0.1 fs² precision and 1 fs² accuracy, as well as the refractivity of the 3ν₁ +ν₃ absorption band of CO₂ with 5 × 10^‒12 precision. This opens up for broadband refractive index metrology and calibration-free spectroscopy of entire molecular bands.

The whispering-gallery-mode (WGM) laser is a type of laser that has an exceptionally narrow linewidth. Noise-immune cavity-enhanced optical heterodyne molecular spectrometry, which is a detection technique with extraordinary properties that benefit from narrow linewidth lasers, has been realized with a WGM laser. By locking to a cavity with a finesse of 55 000, acetylene and carbon dioxide could be simultaneously detected down to an unprecedented noise equivalent absorption per unit length of 6.6 x 10(-14) cm(-1) over 150 s, corresponding to 5 ppt of C2H2.