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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. [ABSTRACT FROM AUTHOR]

The amplitude modulation of a pump field and the phase-sensitive detection of a pump-induced intensity change of a probe field encompass a common practice in nonlinear spectroscopies to enhance the detection sensitivity. A drawback of this approach arises when the modulation frequency is comparable to the width of the spectral feature of interest, since the presence of sidebands in the amplitude-modulated pump field provides distortion to the observed spectral lineshape. This represents a problem when accurate measurements of spectral lineshapes and line positions are pursued, as recently happened in our group with the metrology of the Q(1) line in the 1-0 band of molecular hydrogen. The measurement was performed with a Stimulated Raman Scattering spectrometer that was calibrated, for the first time, against an optical frequency comb. In this work, we develop an analytical tool for nonlinear Stimulated Raman spectroscopies that allows us to precisely quantify spectral distortions arising from high-frequency amplitude modulation in one of the interacting fields. Once they are known, spectral distortions can be deconvolved from the measured spectra to retrieve unbiased data. The application of this tool to the measured spectra is discussed. [ABSTRACT FROM AUTHOR]

We discuss layout and performance of a high-resolution Stimulated Raman Loss spectrometer that has been newly developed for accurate studies of spectral lineshapes and line centre frequencies of hydrogen isotopologues and in general of Raman active transitions. Thanks to the frequency comb calibration of the detuning between pump and Stokes lasers and to an active alignment of the two beams, the frequency accuracy is at a level of 50 kHz. Over the vertical axis the spectrometer benefits from shot-noise limited detection, signal enhancement via multipass cell, active flattening of the spectral baseline and measurement times of few seconds over spectral spans larger than 10 GHz. Under these conditions an efficient averaging of Raman spectra is possible over long measurement times with minimal distortion of spectral lineshapes. By changing the pump laser, transitions can be covered in a very broad frequency span, from 50 to 5000 cm−1, including both vibrational and rotational bands. The spectrometer has been developed for studies of fundamental and collisional physics of hydrogen isotopologues and has been recently applied to the metrology of the Q(1) 1–0 line of H2. [ABSTRACT FROM AUTHOR]

Frequency combs have revolutionized optical frequency metrology, allowing one to determine highly accurate transition frequencies of a wealth of molecular species. These progresses have only marginally benefited infrared-inactive transitions, due to their inherently weak cross-sections. Here we overcome this limitation by introducing stimulated-Raman-scattering metrology, where a frequency comb is exploited to calibrate the frequency detuning between the pump and Stokes excitation lasers. We apply this approach to the investigation of molecular hydrogen, which is a recognized benchmark for tests of quantum electrodynamics and of theories that describe physics beyond the standard model. Specifically, we measure the transition frequency of the Q(1) fundamental line of H2 around 4155 cm−1 with few parts-per-billion uncertainty, which is comparable to the theoretical benchmark of ab initio calculations and more than a decade better than the experimental state of the art. Our comb-calibrated stimulated Raman scattering spectrometer extends the toolkit of optical frequency metrology as it can be applied, with simple technical changes, to many other infrared-inactive transitions, over a 50-5000 cm−1 range that covers also purely rotational bands. Molecular hydrogen has a simple structure that makes it a unique benchmark for molecular quantum physics. The authors determined the transition energy of its fundamental Q(1) vibrational line with an unprecedented parts-per-billion accuracy by a novel spectrometer that combines Stimulated-Raman-Scattering with comb calibration of optical frequencies. [ABSTRACT FROM AUTHOR]

Vernier spectroscopy is a frequency comb-based technique employing optical cavities for filtering of the comb and for enhancement of the interaction length with the sample. Depending on the ratio of the cavity free spectral range and the comb repetition rate, the cavity transmits either widely spaced individual comb lines (comb-resolved Vernier spectroscopy) or groups of comb lines, called Vernier orders (continuous-filtering Vernier spectroscopy, CF-VS). The cavity filtering enables the use of low-resolution spectrometers to resolve the individual comb lines or Vernier orders. Vernier spectroscopy has been implemented using various near- and mid-infrared comb sources for applications ranging from trace gas detection to precision spectroscopy. Here, we present the principles of the technique and provide a review of previous demonstrations of comb-resolved and continuous-filtering Vernier spectroscopy. We also demonstrate two new implementations of CF-VS: one in the mid-infrared, based on a difference frequency generation comb source, with a new and more robust detection system design, and the other in the near-infrared, based on a Ti:sapphire laser, reaching high sensitivity and the fundamental resolution limit of the technique. [ABSTRACT FROM AUTHOR]

We present a continuous-filtering Vernier spectrometer operating in the 3.15-3.4 µm 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 to detect 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 a calibrated CH gas sample as well as dry and laboratory air and extract CH and HO concentrations by multiline fitting of model spectra. The figure of merit of the spectrometer is 1.7 × 10 cm Hz per spectral element and the minimum detectable concentration of CH is 360 ppt Hz, averaging down to 90 ppt after 16 s. [ABSTRACT FROM AUTHOR]