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Nitrous oxide is a long-lived greenhouse gas. Its isotopic composition provides valuable insights into sources and sinks, and about the mechanism of formation. A major challenge in the spectroscopic analysis of the isotopocule compositions is the availability of accurate spectroscopic parameters, particularly for the minor $^{15}$N isotopocules. In this work, we introduce high-resolution spectroscopic measurements of four isotopocules of nitrous oxide: $^{14}$N$_{2}$O, $^{14}$N$^{15}$NO, $^{15}$N$^{14}$NO, and $^{15}$N$_{2}$O in the mid-infrared range of 3300 - 3550 cm$^{-1}$, using a frequency comb-based Fourier transform spectrometer. The nitrous oxide samples were obtained from a chemical synthesis involving acid-catalyzed amine-borane reduction of equimolar amounts of $^{15}$N isotopically enriched sodium nitrite and $^{14}$N sodium nitrite. The high-resolution spectra, measured in a temperature-controlled single-pass absorption cell, were used to retrieve line center frequencies and relative intensities for a total of 426 rovibrational transitions of the ${\nu}$$_{1}$ + ${\nu}$$_{3}$ band of the four isotopocules, and of the one order of magnitude weaker 2${\nu}$$_{2}$ + ${\nu}$$_{3}$ and ${\nu}$$_{1}$ + ${\nu}$$_{2}$ + ${\nu}$$_{3}$ - ${\nu}$$_{2}$ bands in the same spectral region. We compare the determined line center frequencies and relative intensities with spectroscopic parameters available in high-resolution molecular databases. For $^{14}$N$_{2}$O, $^{14}$N$^{15}$NO and $^{15}$N$^{14}$NO we find good agreement with the HITRAN database. The $^{15}$N$_{2}$O isotopocule is missing in HITRAN, and we find that its line center frequencies in the GEISA database, the Institute of Atmospheric Optics database, as well as the Ames-1 line list deviate severely from the comb measurements.

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.

The goal of this white paper is to provide a snapshot of the data availability and data needs primarily for the Ariel space mission, but also for related atmospheric studies of exoplanets and brown dwarfs. It covers the following data-related topics: molecular and atomic line lists, line profiles, computed cross-sections and opacities, collision-induced absorption and other continuum data, optical properties of aerosols and surfaces, atmospheric chemistry, UV photodissociation and photoabsorption cross-sections, and standards in the description and format of such data. These data aspects are discussed by addressing the following questions for each topic, based on the experience of the "data-provider" and "data-user" communities: (1) what are the types and sources of currently available data, (2) what work is currently in progress, and (3) what are the current and anticipated data needs. We present a GitHub platform for Ariel-related data, with the goal to provide a go-to place for both data-users and data-providers, for the users to make requests for their data needs and for the data-providers to link to their available data. Our aim throughout the paper is to provide practical information on existing sources of data whether in databases, theoretical, or literature sources., Comment: 58 pages, submitted to RAS Techniques and Instruments (RASTI). The authors welcome feedback: corresponding author emails can be found as footnotes on page 2

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 use optical frequency comb Fourier transform spectroscopy to record high-resolution, low-pressure, room-temperature spectra of formaldehyde (H$_2$$^{12}$C$^{16}$O) in the range of 1250 to 1390 cm$^{-1}$. Through line-by-line fitting, we retrieve line positions and intensities of 747 rovibrational transitions: 558 from the ${\nu}_6$ band, 129 from the ${\nu}_4$ band, and 14 from the ${\nu}_3$ band, as well as 46 from four different hot bands. We incorporate the accurate and precise line positions (0.4 MHz median uncertainty) into the MARVEL (measured active vibration-rotation energy levels) analysis of the H$_2$CO spectrum. This increases the number of MARVEL-predicted energy levels by 82 and of rovibrational transitions by 5382, and substantially reduces uncertainties of MARVEL-derived H$_2$CO energy levels over a large range: from pure rotational levels below 200 cm$^{-1}$ up to multiply excited vibrational levels at 6000 cm$^{-1}$. This work is an important step toward filling the gaps in formaldehyde data in the HITRAN database.

We present a new spectral analysis of the ${\nu}_1$ and ${\nu}_3$+${\nu}_1$-${\nu}_3$ bands of $^{12}$CH$_3$I around 2971 cm$^{-1}$ based on a high-resolution spectrum spanning from 2800 cm$^{-1}$ to 3160 cm$^{-1}$, measured using an optical frequency comb Fourier transform spectrometer. From this spectrum, we previously assigned the ${\nu}_4$ and ${\nu}_3$+${\nu}_4$-${\nu}_3$ bands around 3060 cm$^{-1}$ using PGOPHER, and the line list was incorporated in the HITRAN database. Here, we treat the two fundamental bands, ${\nu}_1$ and ${\nu}_4$, together with the perturbing states, 2${\nu}_2$+${\nu}_3$ and ${\nu}_2$+2${\nu}_6$$^{\pm2}$, as a four-level system connected via Coriolis and Fermi interactions. A similar four-level system is assumed to connect the ${\nu}_3$+${\nu}_1$-${\nu}_3$ and ${\nu}_3$+${\nu}_4$-${\nu}_3$ hot bands, which appear due to the population of the low-lying ${\nu}_3$ state at room temperature, with the 2${\nu}_2$+2${\nu}_3$ and ${\nu}_2$+${\nu}_3$-${\nu}_6$$^{\pm2}$ perturbing states. This treatment provides a good global agreement of the simulated spectra with experiment, and hence accurate line lists and band parameters of the four connected vibrational states in each system. Overall, we assign 4665 transitions in the fundamental band system, with an average error of 0.00071 cm$^{-1}$, a factor of two better than earlier work on the ${\nu}_1$ band using conventional Fourier transform infrared spectroscopy. The ${\nu}_1$ band shows hyperfine splitting, resolvable for transitions with J $\le$ 2 x K. Finally, the spectral intensities of 65 lines of the ${\nu}_1$ band and 7 lines of the ${\nu}_3$+${\nu}_1$-${\nu}_3$ band are reported for the first time using the Voigt line shape as a model in multispectral fitting.

We use a Fourier transform spectrometer based on a difference frequency generation optical frequency comb to measure high-resolution, low-pressure, room-temperature spectra of methane in the 1250 - 1380 cm$^{-1}$ range. From these spectra, we retrieve line positions and intensities of 678 lines of two isotopologues: 157 lines from the $^{12}$CH${_4}$ ${\nu}$${_4}$ fundamental band, 131 lines from the $^{13}$CH${_4}$ ${\nu}$${_4}$ fundamental band, as well as 390 lines from two $^{12}$CH${_4}$ hot bands, ${\nu}$${_2}$ + ${\nu}$${_4}$ - ${\nu}$${_2}$ and 2${\nu}$${_4}$ - ${\nu}$${_4}$. For another 165 lines from the $^{12}$CH${_4}$ ${\nu}$${_4}$ fundamental band we retrieve line positions only. The uncertainties of the line positions range from 0.19 to 2.3 MHz, and their median value is reduced by a factor of 18 and 59 compared to the previously available data for the $^{12}$CH${_4}$ fundamental and hot bands, respectively, obtained from conventional FTIR absorption measurements. The new line positions are included in the global models of the spectrum of both methane isotopologues, and the fit residuals are reduced by a factor of 8 compared to previous absorption data, and 20 compared to emission data. The experimental line intensities have relative uncertainties in the range of 1.5 - 7.7%, similar to those in the previously available data; 235 new $^{12}$CH${_4}$ line intensities are included in the global model.

We use a Fourier transform spectrometer based on a compact mid-infrared difference frequency generation comb source to perform broadband high-resolution measurements of nitrous oxide, $^{14}$N$_2$$^{16}$O, and retrieve line center frequencies of the $\nu$$_1$ fundamental band and the $\nu$$_1$ + $\nu$$_2$ - $\nu$$_2$ hot band. The spectrum spans 90 cm$^{-1}$ around 1285 cm$^{-1}$ with a sample point spacing of 3 ${\times}$ 10$^{-4}$ cm$^{-1}$ (9 MHz). We report line positions of 72 lines in the $\nu$$_1$ fundamental band between P(37) and R(38), and 112 lines in the $\nu$$_1$ + $\nu$$_2$ - $\nu$$_2$ hot band (split into two components with e/f rotationless parity) between P(34) and R(33), with uncertainties in the range of 90-600 kHz. We derive upper state constants of both bands from a fit of the effective ro-vibrational Hamiltonian to the line center positions. For the fundamental band, we observe excellent agreement in the retrieved line positions and upper state constants with those reported in a recent study by AlSaif et al. using a comb-referenced quantum cascade laser [J Quant Spectrosc Radiat Transf, 2018;211:172-178]. We determine the origin of the hot band with precision one order of magnitude better than previous work based on FTIR measurements by Toth [http://mark4sun.jpl.nasa.gov/n2o.html], which is the source of the HITRAN2016 data for these bands.

We report the design of a microstructured silica-based fiber for widely tunable soliton self-frequency shift, suitable for pumping with two most common fiber laser wavelengths: 1.04 {\mu}m and 1.55 {\mu}m. Depending on the pump source, the output spectrum can be continuously tuned up to 1.67 {\mu}m (pump at 1.04 {\mu}m) or 1.95 {\mu}m (pump at 1.55 {\mu}m) in the same 1.5 m-long fiber sample, with pump-to-soliton conversion efficiency higher than 20%. The fiber is highly birefringent, which results in an excellent polarization extinction ratio of the soliton, reaching 26 dB. The shifted solitons have a high degree of coherence confirmed by pulse-to-pulse interference measurement. The available soliton tuning range covers the wavelengths inaccessible for fiber lasers, e.g., 1.3 {\mu}m and 1.7 {\mu}m, highly important for multi-photon microscopy and imaging. Our work shows that it is possible to design and fabricate one universal optical fiber that supports soliton shift when pumped at two different wavelengths separated by over 500 nm.

We use optical frequency comb Fourier transform spectroscopy to measure high-resolution spectra of iodomethane, CH$_3$I in the C-H stretch region from 2800 to 3160 cm$^{-1}$. The fast-scanning Fourier transform spectrometer with auto-balanced detection is based on a difference frequency generation comb with repetition rate, f$_{rep}$, of 125 MHz. A series of spectra with sample point spacing equal to f$_{rep}$ are measured at different f$_{rep}$ settings and interleaved to yield sampling point spacing of 11 MHz. Iodomethane is introduced into a 76 m long multipass absorption cell by its vapor pressure at room temperature. The measured spectrum contains three main ro-vibrational features: the parallel vibrational overtone and combination bands centered around 2850 cm$^{-1}$, the symmetric stretch ${\nu}_1$ band centered at 2971 cm$^{-1}$, and the asymmetric stretch ${\nu}_4$ band centered at 3060 cm$^{-1}$. The spectra of the ${\nu}_4$ band and the nearby ${\nu}_3$+${\nu}_4$-${\nu}_3$ hot band are simulated using PGOPHER and a new assignment of these bands is presented. The resolved ro-vibrational structures are used in a least square fit together with the microwave data to provide the upper state parameters. We assign 2603 transitions to the ${\nu}_4$ band with standard deviation (observed - calculated) of 0.00034 cm$^{-1}$, and 831 transitions to the ${\nu}_3$+${\nu}_4$-${\nu}_3$ hot band with standard deviation of 0.00084 cm$^{-1}$. The hyperfine splittings due to the ${^{127}}$I nuclear quadrupole moment are observed for transitions with J$\leq$2xK. Finally, intensities of 157 isolated transitions in the ${\nu}_4$ band are reported for the first time using the Voigt line shape as a model in multispectral fitting.

We report the design and characteristics of a simple and compact mode-locked Er-doped fiber laser and its application to broadband cavity-enhanced spectroscopy. The graphene mode-locked polarization maintaining oscillator is thermally stabilized and equipped with three actuators that control the repetition rate: fast and slow fiber stretchers, and metal-coated fiber section. This allows wide tuning of the repetition rate and its stabilization to an external reference source. The applicability of the laser to molecular spectroscopy is demonstrated by detecting CO2 in air using continuous-filtering Vernier spectroscopy.

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 report the first photoacoustic detection scheme using an optical frequency comb - the optical frequency comb photoacoustic spectroscopy (OFC-PAS). OFC-PAS combines the broad spectral coverage and the high resolution of OFCs with the small sample volume of cantilever-enhanced PA detection. In OFC-PAS, a Fourier transform spectrometer (FTS) is used to modulate the intensity of the exciting comb source at a frequency determined by its scanning speed. One of the FTS outputs is directed to the PA cell and the other is measured simultaneously with a photodiode and used to normalize the PA signal. The cantilever-enhanced PA detector operates in a non-resonant mode, enabling detection of broadband frequency response. The broadband and the high-resolution capabilities of OFC-PAS are demonstrated by measuring the rovibrational spectra of the fundamental C-H stretch band of CH${_4}$, with no instrumental line shape distortions, at total pressures of 1000 mbar, 650 mbar, and 400 mbar. In this first demonstration, a spectral resolution two orders of magnitude higher than previously reported with broadband PAS is obtained, limited by the pressure broadening. A limit of detection of 0.8 ppm of methane in N${_2}$ is accomplished in a single interferogram measurement (200 s measurement time, 1000 MHz resolution, 1000 mbar total pressure) for an exciting power spectral density of 42 {\mu}W/cm${^{-1}}$. A normalized noise equivalent absorption of 8x10${^{-10}}$ W cm${^{-1}}$ Hz${^{-1/2}}$ is obtained, which is only a factor of three higher than the best reported with PAS based on continuous wave lasers. A wide dynamic range of up to four orders of magnitude and a very good linearity (limited by the Beer-Lambert law) over two orders of magnitude are realized. OFC-PAS extends the capability of optical sensors for multispecies trace gas analysis in small sample volume with high resolution and selectivity.

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 demonstrate optical frequency comb Faraday rotation spectroscopy (OFC-FRS) for broadband interference-free detection of paramagnetic species. The system is based on a femtosecond doubly resonant optical parametric oscillator and a fast-scanning Fourier transform spectrometer (FTS). The sample is placed in a DC magnetic field parallel to the light propagation. Efficient background suppression is implemented via switching the direction of the field on consecutive FTS scans and subtracting the consecutive spectra, which enables long term averaging. In this first demonstration, we measure the entire Q- and R-branches of the fundamental band of nitric oxide in the 5.2-5.4 {\mu}m range and achieve good agreement with a theoretical model.

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.

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.

Noise-immune cavity-enhanced optical frequency comb spectroscopy (NICE-OFCS) is a recently developed technique that utilizes phase modulation to obtain immunity to frequency-to-amplitude noise conversion by the cavity modes and yields high absorption sensitivity over a broad spectral range. We describe the principles of the technique and discuss possible comb-cavity matching solutions. We present a theoretical description of NICE-OFCS signals detected with a Fourier transform spectrometer (FTS), and validate the model by comparing it to experimental CO2 spectra around 1575 nm. Our system is based on an Er:fiber femtosecond laser locked to a cavity and phase-modulated at a frequency equal to a multiple of the cavity free spectral range (FSR). The NICE-OFCS signal is detected by a fast-scanning FTS equipped with a high-bandwidth commercial detector. We demonstrate a simple method of passive locking of the modulation frequency to the cavity FSR that significantly improves the long term stability of the system, allowing averaging times on the order of minutes. Using a cavity with a finesse of ~9000 we obtain absorption sensitivity of 6.4 x 10^{-11} cm^{-1} Hz^{-1/2} per spectral element, and concentration detection limit for CO2 of 450 ppb Hz^{-1/2}, determined by multiline fitting., Comment: submitted to the FLAIR2014 special issue of Applied Physics B

We demonstrate the first cavity-enhanced optical frequency comb spectroscopy in the mid-infrared wavelength region and report the sensitive real-time trace detection of hydrogen peroxide in the presence of a large amount of water. The experimental apparatus is based on a mid-infrared optical parametric oscillator synchronously pumped by a high power Yb:fiber laser, a high finesse broadband cavity, and a fast-scanning Fourier transform spectrometer with autobalancing detection. The comb spectrum with a bandwidth of 200 nm centered around 3.75 {\mu}m is simultaneously coupled to the cavity and both degrees of freedom of the comb, i.e., the repetition rate and carrier envelope offset frequency, are locked to the cavity to ensure stable transmission. The autobalancing detection scheme reduces the intensity noise by a factor of 300, and a sensitivity of 5.4 {\times} 10^-9 cm^-1 Hz^-1/2 with a resolution of 800 MHz is achieved (corresponding to 6.9 {\times} 10^-11 cm^-1 Hz^-1/2 per spectral element for 6000 resolved elements). This yields a noise equivalent detection limit for hydrogen peroxide of 8 parts-per-billion (ppb); in the presence of 2.8% of water the detection limit is 130 ppb. Spectra of acetylene, methane and nitrous oxide at atmospheric pressure are also presented, and a line shape model is developed to simulate the experimental data., Comment: submitted to special FLAIR 2011 issue of Appl. Phys. B

We achieve a quantum-noise-limited absorption sensitivity of 1.7/times10$^{-12}$ cm$^{-1}$ per spectral element at 400 s of acquisition time with cavity-enhanced frequency comb spectroscopy, the highest demonstrated for a comb-based technique. The system comprises a frequency comb locked to a high-finesse cavity and a fast-scanning Fourier transform spectrometer with an ultra-low-noise autobalancing detector. Spectra with a signal-to-noise ratio above 1000 and a resolution of 380 MHz are acquired within a few seconds. The measured absorption lineshapes are in excellent agreement with theoretical predictions., Comment: 18 pages, 4 figures; http://prl.aps.org/pdf/PRL/v107/i23/e233002

Optical frequency-comb-based-high-resolution spectrometers offer enormous potential for spectroscopic applications. Although various implementations have been demonstrated, the lack of suitable mid-infrared comb sources has impeded explorations of molecular fingerprinting. Here we present for the first time a frequency-comb Fourier transform spectrometer operating in the 2100-to-3700-cm-1 spectral region that allows fast and simultaneous acquisitions of broadband absorption spectra with up to 0.0056 cm-1 resolution. We demonstrate part-per-billion detection limits in 30 seconds of integration time for various important molecules including methane, ethane, isoprene, and nitrous oxide. Our system enables precise concentration measurements even in gas mixtures that exhibit continuous absorption bands, and it allows detection of molecules at levels below the noise floor via simultaneous analysis of multiple spectral features. This system represents a near real-time, high-resolution, high-bandwidth mid-infrared spectrometer which is ready to replace traditional Fourier transform spectrometers for many applications in trace gas detection, atmospheric science, and medical diagnostics., Comment: 23 pages (double spaced), 5 figures, 1 table