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We present a novel approach to cavity ring-down spectroscopy utilizing an optical frequency comb as the direct probe of the Fabry-Perot cavity, coupled with a time-resolved Fourier transform spectrometer for parallel retrieval of ring-down events. Our method achieves high spectral resolution over a broad range, enabling precision measurements of cavity losses and absorption lineshapes with enhanced sensitivity. A critical advancement involves a stabilization technique ensuring complete extinction of comb light without compromising cavity stabilization. We demonstrate the capabilities of our system through precision spectroscopy of carbon monoxide rovibrational transitions perturbed by argon.

We use optical-optical double-resonance (OODR) spectroscopy with a continuous wave (CW) pump and a cavity-enhanced frequency comb probe to measure high rotational energy levels of methane in the upper part of the triacontad polyad (P6). A high-power CW optical parametric oscillator, tunable around 3000 cm$^{-1}$, is consecutively locked to the P(7, A$_2$), Q(7, A$_2$), R(7, A$_2$), and Q(6, F$_2$) transitions in the ${\nu}$$_3$ band, and a comb covering the 5800-6100 cm$^{-1}$ range probes sub-Doppler ladder-type transitions from the pumped levels with J' = 6 to 8, respectively. We report 118 probe transitions in the 3${\nu}$$_3$ $\leftarrow$ ${\nu}$$_3$ spectral range with uncertainties down to 300 kHz (1 x 10$^{-5}$ cm$^{-1}$), reaching 84 unique final states in the 9070-9370 cm$^{-1}$ range with rotational quantum numbers J between 5 and 9. We assign these states using combination differences and by comparison to theoretical predictions from a new ab initio-based effective Hamiltonian and dipole moment operator. This is the first line-by-line experimental verification of theoretical predictions for these hot-band transitions, and we find a better agreement of transition wavenumbers with the new calculations compared to the TheoReTS/HITEMP and ExoMol databases. We also compare the relative intensities and find an overall good agreement with all three sets of predictions. Finally, we report the wavenumbers of 27 transitions in the 2${\nu}$$_3$ spectral range, observed as V-type transitions from the ground state, and compare them to the new Hamiltonian, HITRAN2020, ExoMol and the WKMLC line lists.

Accurate parameters of molecular hot-band transitions, i.e., those starting from vibrationally excited levels, are needed to accurately model high-temperature spectra in astrophysics and combustion, yet laboratory spectra measured at high temperatures are often unresolved and difficult to assign. Optical-optical double-resonance (OODR) spectroscopy allows the measurement and assignment of individual hot-band transitions from selectively pumped energy levels without the need to heat the sample. However, previous demonstrations lacked either sufficient resolution, spectral coverage, absorption sensitivity, or frequency accuracy. Here we demonstrate OODR spectroscopy using a cavity-enhanced frequency comb probe that combines all these advantages. We detect and assign sub-Doppler transitions in the spectral range of the 3${\nu}$${_3}$${\leftarrow}$${\nu}$${_3}$ resonance of methane with frequency precision and sensitivity more than an order of magnitude better than before. This technique will provide high-accuracy data about excited states of a wide range of molecules that is urgently needed for theoretical modeling of high-temperature data and cannot be obtained using other methods., Comment: Addendum added on Aug 20, 2024, containing comparison of experimental line positions and intensities to new predictions from an effective Hamiltonian and the ExoMol database

We demonstrate broadband and sensitive cavity ring-down spectroscopy using a near infrared frequency comb and a time-resolved Fourier transform spectrometer. The cavity decays are measured simultaneously and spectrally sorted, leading to purely exponential decays for each spectral element. The absorption spectra of atmospheric water and carbon dioxide are retrieved and demonstrate the high frequency resolution and absorption precision of the technique. The experimental apparatus, the measurement concept and the data treatment are described. The technique benefits from the advantages of cavity ring-down spectroscopy, i.e. the retrieved absorption does not depend on the cavity parameters, opening up for high accuracy absorption spectroscopy entirely calibration-free.

A new instrument dedicated to the kinetic study of low-temperature gas phase neutral-neutral reactions, including clustering processes, is presented. It combines a supersonic flow reactor with Vacuum Ultra-Violet (VUV) synchrotron photoionization time of flight mass spectrometry. A photoion-photoelectron coincidence detection scheme has been adopted to optimize the particle counting efficiency. The characteristics of the instrument are detailed along with its capabilities illustrated through a few results obtained at low temperatures (< 100 K) including a {photoionization spectrum} of n-butane, the detection of formic acid dimer formation as well as the observation of diacetylene molecules formed by the reaction between the C$_2$H radical and C$_2$H$_2$.

We report the measurement of sub-Doppler double-resonance transitions in methane using a 3.3 $\mu$m continuous wave optical parametric oscillator to pump transitions in the fundamental $\nu_3$ band and a 1.67 $\mu$m frequency comb to probe ladder-type transitions in the 3$\nu_3$ band over 200 cm$^{-1}$ of bandwidth. We detected 36 ladder-type resonances for 9 pumped transitions with average center frequency accuracy of 1.7 MHz, limited by the pump frequency stability. The lines are assigned using the TheoReTS line list, and the intensity ratios for different relative pump/probe polarizations. This method provides accurate assignment of highly excited energy levels that cannot be done using high temperature spectra.

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.

An absorption spectrum of H$_2$$^{16}$O at 1950 K is recorded in a premixed methane/air flat flame using a cavity-enhanced optical frequency comb-based Fourier transform spectrometer. 2417 absorption lines are identified in the 6250 -- 6670 cm region with an accuracy of about 0.01 cm. Absolute line intensities are retrieved using temperature and concentration values obtained by tunable diode laser absorption spectroscopy. Line assignments are made using a combination of empirically known energy levels and predictions from the new POKAZATEL variational line list. 2030 of the observed lines are assigned to 2937 transitions, once blends are taken into account. 126 new energy levels of H$_2$$^{16}$O are identified. The assigned transitions belong to 136 bands and span rotational states up to $J=27$., Comment: 26 pages, 4 figures, 2 tables

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 cavity modes spanning 16 THz of bandwidth in terms of center frequency, linewidth, and amplitude. We retrieve the group delay dispersion of the cavity mirror coatings and pure N${_2}$ with 0.1 fs${^2}$ precision and 1 fs${^2}$ accuracy, as well as the refractivity of the 3{\nu}1+{\nu}3 absorption band of CO${_2}$ with 5 x 10${^{-12}}$ precision. This opens up for broadband refractive index metrology and calibration-free spectroscopy of entire molecular bands.

We demonstrate a broadband mid-infrared (MIR) frequency comb source based on difference frequency generation (DFG) in periodically poled lithium niobate (PPLN) crystal. Mid-infrared radiation is obtained via mixing of the output of a 125 MHz repetition rate Yb-doped fiber laser with Raman-shifted solitons generated from the same source in a highly nonlinear fiber. The resulting idler is tunable in the range of 2.7 - 4.2 {\mu}m with average output power reaching 237 mW, and pulses as short as 115 fs. The coherence of the MIR comb is confirmed by spectral interferometry and heterodyne beat measurements. Applicability of the developed DFG source for laser spectroscopy is demonstrated by measuring absorption spectrum of acetylene at 3.0 - 3.1 {\mu}m.

We present a continuous-filtering Vernier spectrometer operating in the 3.15-3.4 ${\mu}$m range, based on a femtosecond doubly resonant optical parametric oscillator, a cavity with a finesse of 340, a grating mounted on a galvo scanner and two photodiodes. The spectrometer allows acquisition of one spectrum spanning 250 nm of bandwidth in 25 ms with 8 GHz resolution, sufficient for resolving molecular lines at atmospheric pressure. An active lock ensures good frequency and intensity stability of the consecutive spectra and enables continuous signal acquisition and efficient averaging. The relative frequency scale is calibrated using a Fabry-Perot etalon or, alternatively, the galvo scanner position signal. We measure spectra of pure CH${_4}$ as well as dry and laboratory air and extract CH${_4}$ and H${_2}$O concentrations by multiline fitting of model spectra. The figure of merit of the spectrometer is 1.7x10${^-}$${^9}$ cm${^-}$${^1}$ Hz${^-}$${^1}$${^/}$${^2}$ per spectral element and the minimum detectable concentration of CH${_4}$ is 360 ppt Hz${^-}$${^1}$${^/}$${^2}$, averaging down to 90 ppt after 16 s.

Broadband precision spectroscopy is indispensable for providing high fidelity molecular parameters for spectroscopic databases. We have recently shown that mechanical Fourier transform spectrometers based on optical frequency combs can measure broadband high-resolution molecular spectra undistorted by the instrumental line shape (ILS) and with a highly precise frequency scale provided by the comb. The accurate measurement of the power of the comb modes interacting with the molecular sample was achieved by acquiring single-burst interferograms with nominal resolution precisely matched to the comb mode spacing. Here we give a full theoretical description of this sub-nominal resolution method and describe in detail the experimental and numerical steps needed to retrieve ILS-free molecular spectra, i.e. with ILS-induced distortion below the noise level. We investigate the accuracy of the transition line centers retrieved by fitting to the absorption lines measured using this method. We verify the performance by measuring an ILS-free cavity-enhanced low-pressure spectrum of the 3{\nu}1+{\nu}3 band of CO2. We observe and quantify collisional narrowing of absorption line shape, for the first time with a comb-based spectroscopic technique. Thus retrieval of line shape parameters with accuracy not limited by the Voigt profile is now possible for entire absorption bands acquired simultaneously.

We present a thorough analysis of the signal line shapes of Fourier transform-based noise-immune cavity-enhanced optical frequency comb spectroscopy (NICE-OFCS). We discuss the signal dependence on the ratio of the modulation frequency, f${_m}$, to the molecular line width, {\Gamma}. We compare a full model of the signals and a simplified absorption-like analytical model that has high accuracy for low f${_m}$/{\Gamma} ratios and is much faster to compute. We verify the theory experimentally by measuring and fitting NICE-OFCS spectra of CO${_2}$ at 1575 nm using a system based on an Er:fiber femtosecond laser and a cavity with a finesse of ~11000.

We present a versatile mid-infrared frequency comb spectroscopy system based on a doubly resonant optical parametric oscillator tunable in the 3-5.4 {\mu}m range and two detection methods, a Fourier transform spectrometer (FTS) and a Vernier spectrometer. Using the FTS with a multipass cell we measure high-precision broadband absorption spectra of CH$_4$ and NO at ~3.3 {\mu}m and ~5.2 {\mu}m, respectively, and of atmospheric species (CH$_4$, CO, CO$_2$ and H$_2$O) in air in the signal and idler wavelength range. The figure of merit of the system is on the order of 10$^{-8}$ cm$^{-1}$ Hz$^{-1/2}$ per spectral element, and multiline fitting yields minimum detectable concentrations of 10-20 ppb Hz$^{-1/2}$ for CH$_4$, NO and CO. For the first time in the mid-infrared, we perform continuous-filtering Vernier spectroscopy using a low finesse enhancement cavity, a grating and a single detector, and measure the absorption spectrum of CH$_4$ and H$_2$O in ambient air at ~3.3 {\mu}m.

We have recently introduced the Vernier-based Direct Frequency Comb Cavity-Enhanced Spectroscopy technique and we present the corresponding formalism for quantitative broadband spectroscopy. We achieve high sensitivity and broadband performance by acquiring spectra covering more than 2000 cm$^{-1}$ around 12600 cm$^{-1}$ (800 nm), resolving the 3$\nu$+$\delta$ band of water vapor and the entire A-band of oxygen in ambient air. 31 300 independent spectral elements are acquired at the second time scale with an absorption baseline noise of 2$\times$10$^{-8}$ cm$^{-1}$ providing a merit figure of 1,1.10$^{-10}$ cm$^{-1}$/$\sqrt{Hz}$ with a cavity finesse of 3000 and a cavity round-trip length around 3,3 m. This state-of-the-art performance is reached through a continuous Vernier filtering of a Titanium:Saphire frequency comb with the cavity grid of resonances, obtained when the cavity free spectral range and the laser repetition rate are slightly mismatched. Here, we discuss the effect of the Vernier filtering on the measured absorbtion lineshape and we derive the formalism needed to fit molecular spectra., Comment: 12 pages, 11 figures

Fourier transform spectroscopy based on incoherent light sources is a well-established tool in research fields from molecular spectroscopy and atmospheric monitoring to material science and biophysics. It provides broadband molecular spectra and information about the molecular structure and composition of absorptive media. However, the spectral resolution is fundamentally limited by the maximum delay range ({\Delta}$_{max}$) of the interferometer, so acquisition of high-resolution spectra implies long measurement times and large instrument size. We overcome this limit by combining the Fourier transform spectrometer with an optical frequency comb and measuring the intensities of individual comb lines by precisely matching the {\Delta}$_{max}$ to the comb line spacing. This allows measurements of absorption lines narrower than the nominal (optical path-limited) resolution without ringing effects from the instrumental lineshape and reduces the acquisition time and interferometer length by orders of magnitude.