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We have developed a mid-infrared Doppler-free saturation absorption spectroscopy apparatus using a continuous-wave optical parametric oscillator (CW-OPO). Here we report a comprehensive spectral scan of the Q branch transitions of the ν3=1 band of methane (CH4) with an average line width (FWHM) of 4.5 MHz. The absolute frequency calibration was achieved using previously reported transition frequencies determined using optical frequency combs, while a Fabry-Pérot etalon was used for relative frequency calibration. We report 12 transitions with improved accuracies of ~3 MHz.

Automatic Kr separation apparatus and atom counting enable online monitoring of atmospheric krypton-85 with hourly time resolution.

Fast and accurate quantitative detection of 14CO2 has important applications in many fields. The optical detection method based on the sensitive cavity ring-down spectroscopy technology has great potential. But currently it has difficulties of insufficient sensitivity and susceptibility to absorption of other isotopes/impurity molecules. We propose a stepped double-resonance spectroscopy method to excite 14CO2 molecules to an intermediate vibrationally excited state, and use cavity ring-down spectroscopy to probe them. The two-photon process significantly improves the selectivity of detection. We derive the quantitative measurement capability of double-resonance absorption spectroscopy. The simulation results show that the double-resonance spectroscopy measurement is Doppler-free, thereby reducing the effect of other molecular absorption. It is expected that this method can achieve high-selectivity detection of 14CO2 at the sub-ppt level.

Water vapor absorption in the near-ultraviolet region is essential to describe the energy budget of Earth, but little spectroscopic information is available since it is a challenging spectral region for both experimental and theoretical studies. A continuous-wave cavity ring-down spectroscopic experiment was built to record absorption lines of water vapor around 415 nm. With a minimum detectable absorption coefficient of 4 × 10−10 cm−1, 40 rovibrational transitions of H162O were observed in this work, and 27 of them were assigned to the (224), (205), (710), (304), (093), (125), and (531) vibrational bands. A comparison of line positions and intensities determined in this work to the most recent HITRAN database is presented. Water vapor absorption cross-sections near 415 nm were calculated based on our measurements, which vary between 1 × 10−26 and 5 × 10−26 cm2/molecule. These data will also significantly impact the spectroscopy detection of trace gas species in the near-UV region.

Helium is a prototype three-body system and has long been a model system for developing quantum mechanics theory and computational methods. The fine-structure splitting in the 23P state of helium is considered to be the most suitable for determining the fine-structure constant α in atoms. After more than 50 years of efforts by many theorists and experimentalists, we are now working toward a determination of α with an accuracy of a few parts per billion, which can be compared to the results obtained by entirely different methods to verify the self-consistency of quantum electrodynamics. Moreover, the precision spectroscopy of helium allows determination of the nuclear charge radius, and it is expected to help resolve the ‘proton radius puzzle’. In this review, we introduce the latest developments in the precision spectroscopy of the helium atom, especially the discrepancies among theoretical and experimental results, and give an outlook on future progress.

The study of paleogroundwater on a timescale of several thousands to a million years is interesting both in terms of understanding the aquifer system itself and water resource management. It may also provide valuable information about the paleoclimate. In their seminal work, Loosli and Oeschger (1969) identified 81Kr as an ideal age tracer for paleogroundwater up to one million years old. Since then radiokrypton dating has been a desirable tool. Recent developments in the Atom Trap Trace Analysis method have made radiokrypton dating available to the earth science community at large. In this paper we will show the current status for radiokrypton dating with an emphasis on sample size reduction. The latest advancements have allowed analysis with only 20 kg of water. Moreover, we will review selected studies that have been carried out on some large aquifers with old groundwater around the world using this new tool.

We demonstrate fast analysis of

International audience; We investigate collisional line-shape effects that are present in highly accurate experimental spectra of the 3-0 S(1) and 2-0 Q(1) molecular hydrogen absorption lines perturbed by helium. We clearly distin-guish the influence of six different collisional effects (i.e.: collisional broadening and shift, their speed dependencies and the complex Dicke effect) on the shapes of H-2 lines. We demonstrate that only a very specific combination of these six contributions, determined from our ab initio calculations, gives unprece-dentedly good agreement with experimental spectra. If any of the six contributions is neglected, then the experiment-theory comparison deteriorates at least several times. We also analyze the influence of the centrifugal distortion on our ab initio calculations and we demonstrate that the inclusion of this effect slightly improves the agreement with the experimental spectra. (C) 2021 The Author(s). Published by Elsevier Ltd.

Quantitative determination of atmospheric CO2 concentration by remote sensing relies on accurate line parameters. Lamb dips of the lines up to J′′ = 72 in the 30013–00001 band at 1605 nm were measured using a comb-locked cavity ring-down spectrometer, and the positions were determined with an accuracy of a few kHz. A simple effective Hamiltonian model can fit the rotational energies in the 30013 state ideally within the experimental accuracy, indicating that the vibrational state is well-isolated and can be regarded as free from perturbations. From a comparison between other bands using a similar analysis, we conclude that the transitions in the 30013–00001 band could be more suitable as reference lines for sensing applications with the potentially improved line parameter accuracy.

The noble gas radioisotopes 85Kr, 81Kr, and 39Ar are nearly ideal environmental tracers because of their chemical inertness and simple transport mechanisms. Recent advances in Atom Trap Trace Analysis have enabled measurements of 85Kr and 81Kr using 10-20 kg of water or ice, and 39Ar in only a few kilograms, making these tracers available to be applied in the earth sciences on a large-scale. To meet the resulting increase in demand, we have developed an automated process for the dual separation of krypton and argon from environmental samples based on titanium gettering and gas chromatography. 0.5-4 L STP air samples have been purified, demonstrating purities and recoveries of >90% for krypton and >99% for argon within 90-120 min of processing time. Samples of high methane admixtures, a challenge regularly encountered in groundwater applications, have been purified by exploiting the full potential of titanium gettering at high temperatures (>1000 °C). Samples with 0.4-48 L STP of methane admixture are processed in 2-5 h without compromising purity or recovery. The applicability of the purification system is further demonstrated using actual groundwater samples with carbon dioxide and methane content in the extracted gas up to 16 L STP and 42 L STP, respectively.

The electronic transitions of ytterbium atoms in a solid Xe matrix grown at 4.8 K are investigated. Absorption bands are detected in the regions of the gas-phase 6s2 1S0 → 4f135d6s2 and 6s2 1S0 → 6s6p 1P1 transitions. Both bands indicate that Yb atoms occupy multiple trapping sites, of which three are identified. Emission induced by the 6s2 1S0 → 6s6p 1P1 excitation is found to be concentrated entirely in the region of the 6s6p 3PJ → 6s2 1S0 decay, whereas the singlet emission is completely quenched. Multiple emission peaks are observed and the effects of annealing and prolonged irradiation on their amplitudes are found to be significant and are interpreted as a consequence of Yb population transfer from one type of site to another. Modeling of the ground-state site structure and stability predicts three Yb/Xe occupation types, substitutional (ss), tetravacancy (tv) and hexavacancy (hv), in order of decreasing stability. Their tentative associations with observed absorption and emission features are discussed. Time correlated single photon spectroscopy is used to determine the lifetimes of the individual emission bands. They are found to be different from each other with indications of a mixture of short- and long- lived 6s6p 3PJ fine-structure components and demonstrate distinct temperature dependencies. A dramatic decrease in the lifetime of the emission peak tentatively assigned to the most stable site with temperature is explained by a competition between the radiative and non-radiative decay paths of the 6s6p 3P1 state. The mechanism of the latter can be attributed to electron–phonon coupling as confirmed by a model of the temperature-dependence of the lifetime.The electronic transitions of ytterbium atoms in a solid Xe matrix grown at 4.8 K are investigated. Absorption bands are detected in the regions of the gas-phase 6s2 1S0 → 4f135d6s2 and 6s2 1S0 → 6s6p 1P1 transitions. Both bands indicate that Yb atoms occupy multiple trapping sites, of which three are identified. Emission induced by the 6s2 1S0 → 6s6p 1P1 excitation is found to be concentrated entirely in the region of the 6s6p 3PJ → 6s2 1S0 decay, whereas the singlet emission is completely quenched. Multiple emission peaks are observed and the effects of annealing and prolonged irradiation on their amplitudes are found to be significant and are interpreted as a consequence of Yb population transfer from one type of site to another. Modeling of the ground-state site structure and stability predicts three Yb/Xe occupation types, substitutional (ss), tetravacancy (tv) and hexavacancy (hv), in order of decreasing stability. Their tentative associations with observed absorption and emission features are discu...

The absorption spectrum of nitrous oxide around 1.56 µm has been recorded with Doppler limited resolution by a continuous-wave cavity ring-down spectrometer at room temperature using 15N-enriched samples. The typical sensitivity was at the level of 2 × 10−10 cm−1. In total, 3389 transitions were observed and ro-vibrationally assigned on the basis of the global effective Hamiltonian model for six nitrous oxide isotopologues (14N15N16O, 15N14N16O, 14N15N18O, 15N14N18O, 14N15N17O and 15N14N17O). The band-by-band analysis led to the determination of ro-vibrational parameters of 47 bands, 36 of them were newly observed, and the rotational analysis of 11 others were significantly extended and improved. New sets of the effective Hamiltonian parameters were determined for the 14N15N16O and 15N14N16O isotopic species.

We present radiometric $^{81}$Kr dating results for ice samples collected at the outlets of the Guliya ice cap in the western Kunlun Mountains of the Tibetan Plateau. This first application of $^{81}$Kr dating on mid-latitude glacier ice was made possible by recent advances in Atom Trap Trace Analysis, particularly a reduction in the required sample size down to 1 $\mu$L STP of krypton. Eight ice blocks were sampled from the bottom of the glacier at three different sites along the southern edges. The $^{81}$Kr data yield upper age limits in the range of 15-74 ka (90% confidence level). This is an order of magnitude lower than the ages exceeding 500 ka which the previous $^{36}$Cl data suggest for the bottom of the Guliya ice core. It is also significantly lower than the widely used chronology up to 110 ka established for the upper part of the core based on $\delta^{18}$O in the ice.

Ro-vibrational transitions of the 00°3–00°0 band around 1.52 µm with line intensities in the order of 10−24 to 10−23 cm−1/(molecule·cm−2) have been recorded using a comb-assisted laser-locked cavity ring-down spectrometer with high sensitivity as well as high precision. In total, 88 line positions were determined with a sub-MHz uncertainty (1-σ), better than previous experimental results by 1–2 order of magnitude. N2-induced line shape parameters of 20 isolated transitions were derived by using the Voigt profile and the quadratic Speed-Dependent Voigt profile with relative uncertainties of 1–2% (1-σ). Comparisons of the line parameters determined in this work with literature experimental values are given.

Saturation spectroscopy is frequently used to obtain sub-Doppler measurement of atomic and molecular transitions. Optical resonant cavities can be used to enhance the effective absorption path length, and the laser power inside the cavity as well to saturate very weak ro-vibrational transitions of molecules. Three different cavity-enhanced methods, cavity enhanced absorption spectroscopy, cavity ring-down spectroscopy, and noise-immune cavity enhanced optical heterodyne molecular spectroscopy (NICE-OHMS), were compared by measuring the Lamb dip of a C2H2 line at 1.4 µm using a cavity with a finesse of 120000. The center of the line was determined by different cavity-enhanced methods, each giving a sub-kHz (δν/ν≈10−12) statistical uncertainty. The sensitivity and precision of different methods were analyzed and compared. As demonstrated in this study, the NICE-OHMS method is the most sensitive one, but more investigation on the systematic uncertainty is necessary before its application in metrology studies toward a sub-kHz accuracy.

Cosmogenic

Radioactive

Cavity ring-down spectroscopy (CRDS) is a direct absorption spectroscopy method using a high-finesse optical cavity to enhance the effective absorption path length. Very high sensitivity has been achieved by CRDS devices with a detection limit in the range of 10−7–10−13 cm−1. High sensitivity and relatively compact structure make it very useful for trace gas detection. We present an introduction of the experimental method of CRDS, including the principle, implementation, and performance, and also give a review of applications in trace gas detection using CRDS, in terms of the operation wavelength and the limit of detection for different molecules.

Selective pumping and probing of highly excited states of molecules are essential in various studies but are also challenging because of high density of states, weak transition moments, and lack of precise spectroscopy data. We develop a comb-locked cavity-assisted double-resonance spectroscopy (COCA-DR) method for precision measurements using low-power continuous-wave lasers. A high-finesse cavity locked with an optical frequency comb is used to enhance both the pumping power and the probing sensitivity. As a demonstration, Doppler-free stepwise two-photon absorption spectra of CO2 were recorded by using two milliwatt diode lasers (1.60 and 1.67 μm), and the rotation energies in a highly excited state (CO-stretching quanta = 8) were determined with an unprecedented accuracy of a few kilohertz.

A bright beam of metastable helium atoms is useful in various studies. Laser spectroscopy of helium in an atomic beam can provide a determination of the fine-structure constant and the nuclear charge radius, towards a test of quantum electrodynamics (QED). In these measurements, it is necessary to control not only the internal quantum state but also the translation motion of the helium atom. Here we present a setup producing an intense and speed-adjustable continuous beam of helium atoms. By using a combination of laser cooling, focusing, and deflection, helium atoms are prepared at the single quantum state of ${2}^{\phantom{\rule{0.16em}{0ex}}3}{S}_{1}$ ($m=0$), with a very narrow distribution of the longitudinal speed ($\ensuremath{\delta}{v}_{z}l\ifmmode\pm\else\textpm\fi{}4.5$ m/s). At the same time, we obtain a flux of $1.8\ifmmode\times\else\texttimes\fi{}{10}^{13}$ (atoms/s)/sr with a fractional fluctuation below 0.02%. The atomic-beam quality was investigated by laser spectroscopy, indicating a considerable improvement over those used in previous helium precision-spectroscopy measurements.

Paleoclimate reconstructions from ice core records can be hampered due to the lack of a reliable chronology, especially when the stratigraphy is disturbed and conventional dating methods are not readily applied. The noble gas radioisotopes 81Kr and 39Ar can in these cases provide robust constraints as they yield absolute, radiometric ages. 81Kr (half-life 229 ka) covers the time span from 50-1300 ka, which is particularly relevant for polar ice cores, whereas 39Ar (half-life 269 a) with a dating range of 50-1400 a is suitable for high mountain glaciers. For a long time the use of 81Kr and 39Ar for dating of ice samples was hampered by the lack of a detection technique that can meet its extremely small abundance at a reasonable sample size. Here, we report on 81Kr and 39Ar dating of Antarctic and Tibetan ice cores with the detection method Atom Trap Trace Analysis (ATTA), using 5-10 kg of ice for 81Kr and 2-5 kg for 39Ar. Among others, we measured 81Kr in the lower section of Taldice ice core, which is difficult to date by conventional methods, and in the meteoric bottom of the Vostok ice core in comparison with an age scale derived from hydrate growth. Moreover, we have obtained an 39Ar profile for an ice core from central Tibet in combination with a timescale constructed by layer counting. The presented studies demonstrate how the obtained 81Kr and 39Ar ages can complement other methods in developing an ice core chronology, especially for the bottom part.[1] Z.-T. Lu, Tracer applications of noble gas radionuclides in the geosciences, Earth-Science Reviews 138, 196-214, (2014)[2] C. Buizert, Radiometric 81Kr dating identifies 120,000-year-old ice at Taylor Glacier, Antarctica, Proceedings of the National Academy of Sciences, 111, 6876, (2014)[3] L. Tian, 81Kr Dating at the Guliya Ice Cap, Tibetan Plateau, Geophysical Research Letters, (2019)[4] http://atta.ustc.edu.cn

The absorption spectrum of water vapor enriched in oxygen-17 has been recorded by a continuous-wave cavity ring-down spectrometer (CW-CRDS) at room temperature in the 12,277–12,894 cm−1 region. The typical sensitivity of 2 × 10−10 cm−1 allowed the detection of water vapor transitions with intensities larger than 1 × 10−28 cm−1/(molecule cm−2). In total, more than 3400 lines were observed in the recorded spectra with a typical frequency accuracy of 0.002 cm−1. In which more than 3400 transitions were ro-vibrationally assigned to five water isotopic species (H217O, H216O, H218O, HD16O, and HD17O) using the known empirical energy levels combined with the calculated variational line lists based on the results of Partridge and Schwenke. About 1300 transitions of H217O were assigned, leading to the determination of new energy levels of 17 vibration states. Those assigned H217O transitions are involved with the upper vibration states of (013), (023), (032), (051), (061), (070), (080), (090), (112), (131), (150), (160), (211), (230), (301), (310), and (320). The maximum values of the rotational numbers J and Ka were 16 and 9, respectively. The 5ν1 band of HD17O was assigned for the first time as well. The line positions and energy levels determined in this work were compared with literature, and it shows a significant improvement of the line positions of H217O and HD17O in the 12,277–12,894 cm−1 region.

Groundwater dating by radio-krypton (81Kr; half-life of about 229,000 years) was applied to the sedimentary basin aquifer of the North China Plain (NCP). Krypton gas extracted from deep groundwater in the Coastal Plain was analyzed for 81Kr/Kr ratios by Atom Trap Trace Analysis, which yielded normalized ratios of 0.05 to 0.20, corresponding to groundwater residence times of 0.5–1 million years. Helium isotope compositions were determined on groundwater samples collected from the Central Plain and the Coastal Plain along a flow path of about 200 km. Helium dissolved in the groundwater samples are a mixture of atmospheric, crustal radiogenic and mantle derived sources. Mantle derived 3He contributes up to 30% of the total, and the area of occurrence coincides with zones of previous magmatic/tectonic activities. By contrast, >90% of 4He is derived from crustal reservoirs and correlates with 81Kr ages. The absolute groundwater ages (81Kr) and radiogenic 4He concentrations permit us to calibrate the 4He flux into the aquifer as well as the vertical diffusion rate of 4He to utilize the radiogenic 4He in groundwater as a quantitative age tracer. Previously, groundwater showed 14C activities near the limit of detection (30–40 k yr), in contrast Kr and radiogenic 4He data reveal progressively older ages from the recharge area to the Coastal Plain, from

Lamb-dips of the ro-vibrational lines of 12C2H2 near 789 nm were recorded using cavity ring-down saturation spectroscopy. Calibrated by an optical frequency comb, frequencies of 45 acetylene lines were determined with an accuracy of 1.1 × 10 − 7 cm − 1 ( δ ν / ν = 8 × 10 − 12 ), which is over two orders of magnitude more accurate than previous Doppler-limited studies. An averaged shift of about 0.01 cm − 1 were found by comparing the upper energies obtained in this work to those recently presented by Chubb et al. from a MARVEL analysis.

Thirty well isolated ro-vibrational transitions of the 30011e – 00001e band of 12C16O2 at 1.54 μm have been recorded with a laser-locked cavity ring-down spectrometer. The line intensities were obtained with accuracies better than 0.85%. Comparisons of the line intensities determined in this work with literature experimental values and those from HITRAN2016, AMES, UCL-IAO and CDSD-296 line lists are given.

The radioactive isotope 39Ar is an ideal tracer for ocean ventilation, groundwater flow, and for dating mountain glaciers. With a half-life of 269 years, it covers the age range from a few tens to about 1800 years. We evaluate the input history of the atmospheric 39Ar in the past 2500 years. By measuring the 39Ar/Ar ratios of a modern argon sample and two old argon samples collected in 1959 and 1961, respectively, the anthropogenic contribution to the atmospheric 39Ar in the past 60 years is determined to be less than 15%. The temporal variation of the atmospheric 39Ar in the past 2500 years is calculated based on a cosmic-ray record derived from ice cores and tree rings. It is found that the atmospheric 39Ar/Ar ratio has changed by as much as 17% in that period of time. This input variation has to be taken into account and corrected for in future 39Ar dating applications.

H2 is the most abundant molecule in the universe. It is also the only neutral molecule whose energy levels can be precisely calculated based on quantum electrodynamics and fundamental physical constants without using any adjustable parameters. Precision spectroscopy of the hydrogen molecule is of great importance in astrophysical observation and in testing fundamental physics as well. Here we review the theoretical and experimental spectroscopy studies of the electronic ground state of the hydrogen molecule. The frequency of the R(1) transition in the V =2-0 band of HD is also determined with an accuracy of 5×10−10, which is the most precisely measured ro-vibrational transition of the hydrogen molecule to date. By comparing the calculated and experimental results, we present perspectives of the precision spectroscopy of the hydrogen molecule in the determination of fundamental physical constants such as the proton-electron mass ratio.

Water lines in the infrared are convenient frequency references. We present absolute positions of several H 2 16 O ro-vibrational transitions around 790 nm using comb-locked cavity ring-down saturation spectroscopy. Lamb dips of 6 water lines with saturation power in the range of 70–130 kW/cm 2 were observed and the line positions were determined with an accuracy of 25 kHz, corresponding to a fractional uncertainty of 6.6 × 10 −11 . The present work demonstrates the capability to considerably improve the accuracy of the water line positions in the infrared.

Molecular transitions provide natural frequency standards for spectroscopy, telecommunication, and astrophysics. The frequency accuracy is also crucial in various tests of fundamental physics. A comb-locked cavity ring-down spectrometer measured lamb dips of sixty-one 12C16O transitions around 1.57 μm in the second overtone band. The positions were determined with an accuracy of a few kHz. A new set of rotational spectroscopic parameters was derived with 30 ground state combination difference for the ground vibrational state with a standard deviation of 4.5 kHz. It results in a refinement of the ro-vibrational spectroscopic constants for the v=3 vibrational state. These parameters allow the pure rotational line lists of the υ = 0 ← 0 and υ = 3 ← 3 in the 112 GHz – 3.89 THz regions.

A two-channel thermal dissociation cavity ring down spectroscopy (CRDS) instrument has been built for in situ, real-time measurement of NO2 and total RNO2 (peroxy nitrates and alkyl nitrates) in ambient air, with a NO2 detection limit of 0.10 ppbv at 1 s. A 6-day long measurement was conducted at urban site of Hefei by using the CRDS instrument with a time resolution of 3 s. A commercial molybdenum converted chemiluminescence (Mo-CL) instrument was also used for comparison. The average RNO2 concentration in the 6 days was measured to be 1.94 ppbv. The Mo-CL instrument overestimated the NO2 concentration by a bias of +1.69 ppbv in average, for the reason that it cannot distinguish RNO2 from NO2. The relative bias could be over 100% during the afternoon hours when NO2 was low but RNO2 was high.

Transitions of the 6ν3 overtone band of 14N216O near 775 nm have been studied by continuous-wave cavity ring-down spectroscopy. Line positions and intensities were derived from a fit of the line shape using a hard-collisional profile. The line positions determined with absolute accuracy of 5×10−4 cm−1 allowed us to reveal finer ro-vibrational couplings taking place after J>14 except a strong anharmonic interaction identified by the effective Hamiltonian model. The absolute line intensities have also been retrieved with an estimated accuracy of 2% for a majority of the unblended lines. A new set of ro-vibrational and dipole moment parameters were derived from the experimental values. A comparison between the line positions and intensities of the 6ν3 band obtained in this work and those from previous studies is given.

International audience; Fully quantum ab initio calculations of the collision-induced shapes of two rovibrational H-2 lines perturbed by He provide an unprecedented subpercent agreement with ultra-accurate cavity-enhanced measurements. This level of consistency between theory and experiment hinges on a highly accurate potential energy surface and a realistic treatment of the velocity changing and dephasing collisions. In addition to the fundamental importance, these results show that ab initio calculations can provide reference data for spectroscopic studies of planet atmospheres at the required accuracy level and can be used to populate spectroscopic line-by-line databases.

Temperature dependence of molecular absorption line shape is important information for spectroscopic studies and applications. In this work, we report a comb-locked cavity ring-down spectrometer employing a cryogenic cooler to perform absorption spectroscopy measurements at temperatures between 40 K and 300 K. As a demonstration, we recorded the spectrum of the R(0) line in the (2-0) band of HD at 46 K. The temperature was also confirmed by the Doppler width of the HD line. Spectra of CH4 near 1.394 μm were also recorded in a wide temperature range of 70−300 K. Lower-state energies of methane lines were analyzed by fitting these spectra, which can be directly compared with the HITRAN and TheoReTS databases. Considerable deviations were observed, indicating the need to investigate the assignments of the methane lines in this region.