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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 mechanisms of formation. A major challenge in the spectroscopic analysis of the isotopocule compositions is the availability of accurate spectroscopic parameters, particularly for the minor 15N isotopocules. In this work, we introduce high-resolution spectroscopic measurements of four isotopocules of nitrous oxide: ¹⁴N₂O, ¹⁴N¹⁵NO, ¹⁵N¹⁴NO, and ¹⁵N₂O 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 ¹⁵N isotopically enriched sodium nitrite and ¹⁴N 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 ν1 + ν3 band of the four isotopocules, and of the one order of magnitude weaker 2ν2 + ν3 and ν1 + ν2 + ν3 – ν2 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 ¹⁴N₂O, ¹⁴N¹⁵NO and ¹⁵N¹⁴NO we find good agreement with the HITRAN database. The ¹⁵N₂O 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.

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 cool stars. 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 data bases, theoretical, or literature sources.

We use optical-optical double-resonance spectroscopy with a continuous wave (CW) pump and a cavity-enhanced frequency comb probe to measure the energy levels of methane in the upper part of the triacontad polyad (P6) with higher rotational quantum numbers than previously assigned. A high-power CW optical parametric oscillator, tunable around 3000 cm-1, is consecutively locked to the P(7, A2), Q(7, A2), R(7, A2), and Q(6, F2) transitions in the ν3 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 3ν3 ← ν3 spectral range with uncertainties down to 300 kHz (1 × 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 with 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 2ν3 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.

We present the first mid-infrared optical frequency comb spectrometer employing an absorption cell based on self-fabricated, all-silica antiresonant hollow-core fiber (ARHCF). The spectrometer is capable of measuring sub-mL sample volumes with 26 m interaction length and noise equivalent absorption sensitivity of 8.3 × 10−8 cm−1 Hz−1/2 per spectral element in the range of 2900 cm−1 to 3100 cm−1. Compared to a commercially available multipass cell, the ARHCF offers a similar interaction length in a 1000 times lower gas sample volume and a 2.8 dB lower transmission loss, resulting in better absorption sensitivity. The broad transmission windows of ARHCFs, in combination with a tunable optical frequency comb, make them ideal for multispecies detection, while the prospect of measuring samples in small volumes makes them a competitive technique to photoacoustic spectroscopy along with the robustness and prospect of coiling the ARHCFs open doors for miniaturization and out-of-laboratory applications.

We use optical frequency comb Fourier transform spectroscopy to record high-resolution, low-pressure, room-temperature spectra of formaldehyde (H₂¹²C¹⁶O) 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 ν₆ band, 129 from the ν₄ band, and 14 from the ν₃ 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 H₂CO 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 H₂CO 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.

A procedure for automated low uncertainty assessment of empty cavity mode frequencies in Fabry-Pérot cavity based refractometry that does not require access to laser frequency measuring instrumentation is presented. It requires a previously well-characterized system regarding mirror phase shifts, Gouy phase, and mode number, and is based on the fact that the assessed refractivity should not change when mode jumps take place. It is demonstrated that the procedure is capable of assessing mode frequencies with an uncertainty of 30 MHz, which, when assessing pressure of nitrogen, corresponds to an uncertainty of 0.3 mPa.

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 3ν₃ ← ν₃ 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.

We use optical-optical double-resonance spectroscopy with a high-power continuous wave pump and a cavity-enhanced comb probe to expand sub-Doppler measurements of the 3v3 ← v3 band of CH4 to higher rotational levels. We assign the final states using combination differences, i.e., by reaching the same state using different pump/probe combinations.

We use optical-optical double-resonance spectroscopy with a high-power continuous wave pump and a cavity-enhanced comb probe to expand sub-Doppler measurements of the 3ν3←ν3 band of CH4 to higher rotational levels. We assign the final states using combination differences, i.e., by reaching the same state using different pump/probe combinations.