Assignment of the methanol OH-stretch overtone spectrum using the pattern recognition method.

We present the measurement and analysis of the 2OH stretching band of methanol between 7165 cm-1 and 7230 cm-1 cooled down to 26 ± 12 K in a buffer gas cooling experiment. Measurements were performed with a cavity ring-down spectrometer having a detection limit αmin = 2 × 10-10 cm-1. A total of 350 rovibrational transitions were assigned and 62 rovibrational transitions were tentatively assigned. This assignment was performed using the pattern recognition method developed by Rakvoský et al. [Phys. Chem. Chem. Phys., 2021, 23, 20193-20200]. In this work, we extended their method by using information on the relative intensities of the transitions to add one criterion to the validation of the assignments, allowing us to firmly assign 188 additional rovibrational transitions and to tentatively assign 14 more compared to the ir work.

Frequency stable and low phase noise THz synthesis for precision spectroscopy.

We present a robust approach to generate a continuously tunable, low phase noise, Hz linewidth and mHz/s stability THz emission in the 0.1 THz to 1.4 THz range. This is achieved by photomixing two commercial telecom, distributed feedback lasers locked by optical-feedback onto a single highly stable V-shaped optical cavity. The phase noise is evaluated up to 1.2 THz, demonstrating Hz-level linewidth. To illustrate the spectral performances and agility of the source, low pressure absorption lines of methanol and water vapors have been recorded up to 1.4 THz. In addition, the hyperfine structure of a water line at 556.9 GHz, obtained by saturation spectroscopy, is also reported, resolving spectral features displaying a full-width at half-maximum of 10 kHz. The present results unambiguously establish the performances of this source for ultra-high resolution molecular physics.

The (2-0) R(0) and R(1) transition frequencies of HD determined to a 10-10 relative accuracy by Doppler spectroscopy at 80 K.

The Doppler broadened R(0) and R(1) lines of the (2-0) vibrational band of HD have been measured at liquid nitrogen temperature and at pressures of 2 Pa, with a comb referenced continuous-wave cavity ring-down spectrometer set-up. Transition frequencies of 214905335185 kHz and 217105181898 kHz were derived from 33 and 83 recordings, with corresponding root mean squared deviation of 53 and 33 kHz for the R(0) and R(1) transition, respectively. This is the first sub-MHz frequency determination of the R(0) transition frequency and represents a three order of magnitude accuracy improvement compared to literature. The R(1) transition frequency is in very good agreement with previous determinations in saturation regime reported with similar accuracy. To achieve such accuracy, the transition frequency of the (101)-(000) 211-312 line of H216O interfering with the R(0) line had to be precisely determined and is reported with a standard error of 100 Hz at 214904329826.49(10) kHz (relative uncertainty of 5 × 10-13). These measurement sets provide stringent reference values for validating future advances in the theoretical description of the hydrogen (and water) molecule.

Comb coherence-transfer and cavity ring-down saturation spectroscopy around 1.65 µm: kHz-accurate frequencies of transitions in the 2ν3 band of 12CH4.

Comb Coherence Transfer (CCT) uses a feed-forward frequency correction to transfer the optical phase of a frequency comb to the beam of a free-running diode laser. This allows the amplification of a selected comb tooth by 50 dB while adding agile and accurate frequency tuning. In the present work, SI-traceable frequency calibration and comb tooth narrowing down to 20 kHz is additionally provided by comb frequency locking to an ultrastable optical frequency reference distributed from Paris to Grenoble through the RENATER optical fiber network [Lisdat et al., Nat. Commun., 2016, 7, 12443]. We apply this CCT broadly tunable source for saturated cavity ring-down spectroscopy of ro-vibrational R0 to R10 multiplets in the 2ν3 band of 12CH4 (from 6015 to 6115 cm-1). Indeed, efficient cavity injection with large intra-cavity power build-up induces saturation of the ro-vibrational transitions at low pressure and Doppler-free Lamb dips are observed with high signal/noise. kHz-accurate transition frequencies are derived improving by three orders of magnitude previous values from spectra in the Doppler regime, which are strongly affected by line blending. While previous saturation spectroscopy investigations addressed specific 2ν3 multiplets (R6 or R9), the CCT approach allowed for a rapid coverage of the entire R0-R10 series. Measured transition frequencies are compared with experimental and theoretical line lists available in the literature.

High-temperature hypersonic Laval nozzle for non-LTE cavity ringdown spectroscopy.

A small dimension Laval nozzle connected to a compact high enthalpy source equipped with cavity ringdown spectroscopy (CRDS) is used to produce vibrationally hot and rotationally cold high-resolution infrared spectra of polyatomic molecules in the 1.67 µm region. The Laval nozzle was machined in isostatic graphite, which is capable of withstanding high stagnation temperatures. It is characterized by a throat diameter of 2 mm and an exit diameter of 24 mm. It was designed to operate with argon heated up to 2000 K and to produce a quasi-unidirectional flow to reduce the Doppler effect responsible for line broadening. The hypersonic flow was characterized using computational fluid dynamics simulations, Pitot measurements, and CRDS. A Mach number evolving from 10 at the nozzle exit up to 18.3 before the occurrence of a first oblique shock wave was measured. Two different gases, carbon monoxide (CO) and methane (CH4), were used as test molecules. Vibrational (Tvib) and rotational (Trot) temperatures were extracted from the recorded infrared spectrum, leading to Tvib = 1346 ± 52 K and Trot = 12 ± 1 K for CO. A rotational temperature of 30 ± 3 K was measured for CH4, while two vibrational temperatures were necessary to reproduce the observed intensities. The population distribution between vibrational polyads was correctly described with Tvib I=894±47 K, while the population distribution within a given polyad (namely, the dyad or the pentad) was modeled correctly by Tvib II=54±4 K, testifying to a more rapid vibrational relaxation between the vibrational energy levels constituting a polyad.

Feed-forward comb-assisted coherence transfer to a widely tunable DFB diode laser.

The transfer of phase coherence from an ultrastable master laser to a distributed feedback diode laser, using an optical comb as a transfer oscillator, is obtained via a new scheme allowing continuous scanning across the whole tuning range of the slave laser together with absolute frequency determination. This is accomplished without phase lock loops, through a robust high-bandwidth feed-forward control acting directly on the slave laser output radiation. The correction is obtained by means of a dual-parallel Mach-Zehnder interferometer used as an optical single-sideband modulator. Coherence transfer across a master-slave frequency gap of 14 THz yields an ∼10 kHz linewidth providing high injection efficiency of an optical cavity with finesse 250 000. This allows demonstrating a cavity ring-down absorption spectrum of low-pressure ambient air over a 300 GHz spectral window.

Feed-forward coherent link from a comb to a diode laser: Application to widely tunable cavity ring-down spectroscopy.

We apply a feed-forward frequency control scheme to establish a phase-coherent link from an optical frequency comb to a distributed feedback (DFB) diode laser: This allows us to exploit the full laser tuning range (up to 1 THz) with the linewidth and frequency accuracy of the comb modes. The approach relies on the combination of an RF single-sideband modulator (SSM) and of an electro-optical SSM, providing a correction bandwidth in excess of 10 MHz and a comb-referenced RF-driven agile tuning over several GHz. As a demonstration, we obtain a 0.3 THz cavity ring-down scan of the low-pressure methane absorption spectrum. The spectral resolution is 100 kHz, limited by the self-referenced comb, starting from a DFB diode linewidth of 3 MHz. To illustrate the spectral resolution, we obtain saturation dips for the 2ν3 R(6) methane multiplet at µbar pressure. Repeated measurements of the Lamb-dip positions provide a statistical uncertainty in the kHz range.

Direct, Precise Measurements of Isotopologue Abundance Ratios in CO2 Using Molecular Absorption Spectroscopy: Application to Δ17O.

We present an ultrasensitive absorption spectrometer based on a 30 Hz/s stability, sub-kHz line width laser source coupled to a high-stability cavity-ring-down-spectroscopy setup. It provides direct and precise measurements of the isotopic ratios δ17O and δ18O in CO2. We demonstrate the first optical absorption measurements of 17O anomalies in CO2 with a precision better than 10 ppm, matching the requirements for paleo-environmental applications. This illustrates how optical absorption methods have become a competitive alternative to state-of-the-art isotopic ratio mass spectrometry techniques.

Ab initio variational predictions for understanding highly congested spectra: rovibrational assignment of 108 new methane sub-bands in the icosad range (6280-7800 cm(-1)).

A detailed study of methane spectra in the highly congested icosad range of 6280-7800 cm(-1) has been performed using global variational calculations derived from accurate ab initio potential energy and dipole moment surfaces. About 13,000 (12)CH4 lines of the WKLMC line lists recorded at 80 and 296 K using very sensitive laser techniques (DAS, CRDS) have been rovibrationally assigned from first principles predictions. Overall, a total of 7436 upper energy levels were determined. Among the 20 bands and the 134 sub-levels contained in the icosad system, 20 and 108 have been identified for the first time, respectively. The assigned transitions represent 98% of the sum of the experimental intensity at 80 K. This work demonstrates for the first time how accurate first principles global calculations allow assigning complicated spectra of a molecule with more than 4 atoms.

Communication: Saturated CO2 absorption near 1.6 µm for kilohertz-accuracy transition frequencies.

Doppler-free saturated-absorption Lamb dips were measured on weak rovibrational lines of (12)C(16)O2 between 6189 and 6215 cm(-1) at sub-Pa pressures using optical feedback frequency stabilized cavity ring-down spectroscopy. By referencing the laser source to an optical frequency comb, transition frequencies for ten lines of the 30013←00001 band P-branch and two lines of the 31113←01101 hot band R-branch were determined with an accuracy of a few parts in 10(11). Involving rotational quantum numbers up to 42, the data were used for improving the upper level spectroscopic constants. These results provide a highly accurate reference frequency grid over the spectral interval from 1599 to 1616 nm.

Optical phase cloning by an integrated dual-parallel Mach-Zehnder modulator.

The use of a dual-parallel Mach-Zehnder modulator in a feed-forward configuration is shown to serve the purpose of cloning the optical phase of a master oscillator on a distributed-feed-back (DFB) slave laser exhibiting a multi-MHz-wide frequency noise spectrum. A residual phase error of 113 mrad is obtained together with an extremely high control bandwidth of hundreds of megahertz and a gigahertz-level capture and tuning range. Besides offering a dramatic improvement over feedback loops, this approach is susceptible of hybrid integration in a cost-effective compact device benefiting from the wide tunability of DFB lasers.

Optical feedback frequency stabilized cavity ring-down spectroscopy.

We introduce optical feedback frequency stabilized cavity ring-down spectroscopy (OFFS-CRDS), a near-shot-noise-limited technique that combines kilohertz resolution with an absorption detection sensitivity of 5×10(-13) cm(-1) Hz(-1/2). Its distributed feedback laser source is stabilized to a highly stable V-shaped reference cavity by optical feedback and fine-tuned by means of single-sideband modulation. The stability of this narrow laser is transferred to a ring-down (RD) cavity using a new fibered Pound-Drever-Hall (PDH) locking scheme without a dedicated electro-optic phase modulator, yielding several hundred RD events per second. We demonstrate continuous coverage of more than 7 nm with a baseline noise of 5×10(-12) cm(-1) and a dynamic range spanning six decades. With its resonant intracavity light intensity on the order of 1 kW/cm2, the spectrometer was used for observing a Lamb dip in a transition of carbon dioxide involving four vibrational quanta. Saturating such a weak transition at 160 µW input power, OFFS-CRDS paves the way to Doppler-free molecular overtone spectroscopy for precision measurements of hyperfine structures and pressure shifts.

Optical feedback stabilized laser tuned by single-sideband modulation.

We report a subkilohertz-linewidth distributed-feedback diode laser that is optical-feedback locked to a highly stable V-shaped cavity with drift rates below 20 Hz/s. This source is continuously tunable over 1 THz around 1590 nm by selecting a cavity mode and using an innovative single-sideband modulation scheme, which allows for frequency shifting over up to 40 GHz with millihertz accuracy. This robust setup achieves high performance without advanced vibration isolation and will be a powerful tool for metrological applications, in particular a redetermination of the Boltzmann constant by molecular spectroscopy.

Cavity ring down spectroscopy with 5 × 10(-13) cm-1 sensitivity.

The ultimate sensitivity performances obtained with a continuous wave-cavity ring down spectroscopy setup in the near infrared are investigated. At fixed frequency, the noise of the photodetector is found to be the main limitation and the best limit of detection (about 10(-11) cm(-1)) is reached after a 10 s averaging. We show that long term baseline fluctuations can be efficiently averaged over several days allowing us to reach a detection limit as low as 5 × 10(-13) cm(-1). The achieved sensitivity is illustrated on narrow spectral intervals where the weakest lines detected so far by absorption spectroscopy are observed: (i) ultra-weak transitions of the a(1)Δ(g)(0)-X (3)Σ(g) (-)(1) hot band of (16)O(2) near 1.58 µm and (ii) first detection of an electric quadrupole transition in the second overtone band of nitrogen ((14)N(2)) near 1.44 µm.

Frequency comb based spectrometer for in situ and real time measurements of IO, BrO, NO2, and H2CO at pptv and ppqv levels.

We report an instrument designed for trace gas measurement of highly reactive halogenated radicals, such as bromine oxide and iodine oxide, as well as for nitrogen dioxide and formaldehyde. This compact and robust spectrometer relies on an alternated injection of a frequency-doubled femtosecond radiation at 338 and 436 nm into two parallel high-finesse cavities, for measuring BrO + H(2)CO, and IO + NO(2), respectively. The transmission of the broadband radiation through the cavity is analyzed with a high resolution, compact spectrograph consisting of an echelle grating and a high sensitivity CCD camera. The transportable instrument fits on a breadboard 120 × 60 cm size and is suitable for in situ and real time measurements of these species. A field campaign at the Marine Boundary Layer in Roscoff (in the northwest of France, 48.7°N, 4.0°W) during June 2011 illustrates the outstanding performance of the instrument, which reaches a bandwidth normalized minimum absorption coefficient of 1.3 × 10(-11) cm(-1) Hz(-1/2) per spectral element, and provides detection levels as low as 20 parts per quadrillion of IO in 5 min of acquisition.

The absorption spectrum of D2: ultrasensitive cavity ring down spectroscopy of the (2-0) band near 1.7 µm and accurate ab initio line list up to 24,000 cm(-1).

Eleven very weak electric quadrupole transitions Q(2), Q(1), S(0)-S(8) of the first overtone band of D(2) have been measured by very high sensitivity CW-cavity ring down spectroscopy (CRDS) between 5850 and 6720 cm(-1). The noise equivalent absorption of the recordings is on the order of α(min) ≈ 3 × 10(-11) cm(-1). By averaging a high number of spectra, the noise level was lowered to α(min) ≈ 4 × 10(-12) cm(-1) in order to detect the S(8) transition which is among the weakest transitions ever detected in laboratory experiments (line intensity on the order of 1.8 × 10(-31) cm/molecule at 296 K). A Galatry profile was used to reproduce the measured line shape and derive the line strengths. The pressure shift and position at zero pressure limit were determined from recordings with pressures ranging between 10 and 750 Torr. A highly accurate theoretical line list was constructed for pure D(2) at 296 K. The intensity threshold was fixed to a value of 1 × 10(-34) cm/molecule at 296 K. The obtained line list is provided as supplementary material. It extends up to 24,000 cm(-1) and includes 201 transitions belonging to ten v-0 cold bands (v = 0-9) and three v-1 hot bands (v = 1-3). The energy levels include the relativistic and quantum electrodynamic corrections as well as the effects of the finite nuclear mass. The quadrupole transition moments are calculated using highly accurate adiabatic wave functions. The CRDS line positions and intensities of the first overtone band are compared to the corresponding calculated values and to previous measurements of the S(0)-S(3) lines. The agreement between the CRDS and theoretical results is found within the claimed experimental uncertainties (on the order of 1 × 10(-3) cm(-1) and 2% for the positions and intensities, respectively) while the previous S(0)-S(3) measurements showed important deviations for the line intensities.

The absorption spectrum of H2: CRDS measurements of the (2-0) band, review of the literature data and accurate ab initio line list up to 35000 cm(-1).

Five very weak transitions-O(2), O(3), O(4), O(5) and Q(5)-of the first overtone band of H(2) are measured by very high sensitivity CW-Cavity Ring Down Spectroscopy (CRDS) between 6900 and 7920 cm(-1). The noise equivalent absorption of the recordings is on the order of α(min)≈ 5 × 10(-11) cm(-1) allowing for the detection of the O(5) transition with an intensity of 1.1 × 10(-30) cm per molecule, the smallest intensity value measured so far for an H(2) absorption line. A Galatry profile was used to reproduce the measured line shape and derive the line strengths. The pressure shift of the O(2) and O(3) lines was accurately determined from a series of recordings with pressure ranging between 10 and 700 Torr. From an exhaustive review of the literature data, the list of H(2) absorption lines detected so far has been constructed. It includes a total of 39 transitions ranging from the S(0) pure rotational line near 354 cm(-1) up to the S(1) transition of the (5-0) band near 18,908 cm(-1). These experimental values are compared to a highly accurate theoretical line list constructed for pure H(2) at 296 K (0-35,000 cm(-1), intensity cut off of 1 × 10(-34) cm per molecule). The energy levels and transition moments were computed from high level quantum mechanics calculations. The overall agreement between the theoretical and experimental values is found to be very good for the line positions. Some deviations for the intensities of the high overtone bands (V > 2) are discussed in relation with possible pressure effects affecting the retrieved intensity values. We conclude that the hydrogen molecule is probably a unique case in rovibrational spectroscopy for which first principles theory can provide accurate spectroscopic parameters at the level of the performances of the state of the art experimental techniques.

Accurate determination of low state rotational quantum numbers (J < 4) from planar-jet and liquid nitrogen cell absorption spectra of methane near 1.4 micron.

An improved procedure for accurate determination of empirical lower state rotational quantum numbers from molecular absorption spectra is demonstrated for methane. We combine the high resolution absorption spectra in the 7070-7300 cm(-1) frequency range obtained in liquid nitrogen cooled cryogenic cell (T = 81 K) and in supersonic planar jet expansion (T(R) = 25 K). Empirical lower state energies of 59 transitions are determined from the ratio of the absolute absorption line strengths at 25 and 81 K. The procedure relies on the realistic description of rotational state populations in the supersonic jet expansion where non-equilibrium nuclear spin isomer distributions are generated due to the rapid cooling. The accuracy of the experimental determination of the lower state energies with J < or = 3 is found to considerably improve the results of the same approach applied to spectra at 296 and 81 K. The 59 transitions with determined lower J values provide a good starting point for the theoretical interpretation of the highly congested icosad region of methane. In particular, the centres of nine vibrational bands are estimated from the transitions with J = 0 lower state rotational quantum number.

Development and airborne operation of a compact water isotope ratio infrared spectrometer.

A sensitive laser spectrometer, named IRIS (water isotope ratio infrared spectrometer), was developed for the in situ detection of the isotopic composition of water vapour in the upper troposphere and the lower stratosphere. Isotope ratio measurements can be used to quantify troposphere-stratosphere exchange, and to study the water chemistry in the stratosphere. IRIS is based on the technique of optical feedback cavity-enhanced absorption spectroscopy. It uses a room temperature near-infrared laser, and does not require cryogenic cooling of laser or detectors. The instrument weighs 51 kg including its support structure. Airborne operation was demonstrated during three flights aboard the European M55-Geophysica stratospheric research aircraft, as part of the AMMA/SCOUT-03 (African Monsoon Multidisciplinary Analysis/Stratospheric Climate links with emphasis on the Upper Troposphere and lower stratosphere) campaign in Burkina Faso in August 2006. One-second averaged, vertical profiles of delta(2)H, delta(17)O and delta(18)O in the upper troposphere are shown, as are the delta(17)O-delta(18)O and delta(2)H-delta(18)O relations. The data are discussed with reference to a Rayleigh distillation model. As expected, there is no indication of non-mass-dependent fractionation (also known as mass-independent fractionation) in the troposphere. Furthermore, improvements to the thermal management system and a move to a (cryogen-free) longer-wavelength laser source are discussed, which together should result in approximately two orders of magnitude improvement of the sensitivity.