Accurate absolute frequency measurement of the S(2) transition in the fundamental band of H2 near 2.03 µm.

A series of spectra of the quadrupolar electric S(2) transition of H2 in the 1-0 band near 4917 cm-1 has been recorded at seven pressure values between 2 and 100 Torr. The comb-referenced cavity ring down spectroscopy (CR-CRDS) technique was used for the recording of this very weak transition. The accuracy of the spectrum frequency axis is achieved by linking the CRDS setup to an optical frequency comb referenced to a GPS-referenced 10 MHz rubidium clock. Applying a multi-spectrum fit procedure to the seven averaged spectra with a quadratic speed dependence Nelkin-Ghatak profile, the transition frequency is determined (ν0 = 147 408 142 357 kHz) with an uncertainty of 150 kHz (∼1 × 10-9 in relative). This represents the smallest uncertainty achieved so far for a transition in the fundamental band of H2. The experimental frequency reported in this work is 1.53 MHz higher than the best-to-date theoretical value. This difference represents 1.5 times the 1σ-uncertainty (about 1 MHz) of the calculated frequency. The measurements also allow for the determination of the absolute intensity value of the S(2) line which shows an agreement with the ab initio value at the per mil level. In addition, the cross section of the collision induced absorption (CIA) underlying the S(2) line is accurately retrieved from the quadratic pressure dependence of the baseline level of the recorded spectra.

12CO2 transition frequencies with kHz-accuracy by saturation spectroscopy in the 1.99-2.09 µm region.

Saturation spectroscopy has been used to determine the absolute frequencies of 107 ro-vibrational transitions of the two strongest 12CO2 bands of the 2 µm region. The considered 20012-00001 and 20013-00001 bands are of importance for the CO2 monitoring in our atmosphere. Lamb dips were measured using a cavity ring-down spectrometer linked to an optical frequency comb referenced to a GPS-disciplined Rb oscillator or to an ultra-stable optical frequency. The comb-coherence transfer (CCT) technique was applied to obtain a RF tunable narrow-line comb-disciplined laser source using an external cavity diode laser and a simple electro-optic modulator. This setup allows obtaining transition frequency measurements with kHz-level accuracy. The resulting accurate values of the energy levels of the 20012 and 20013 vibrational states are reproduced with a (1σ)-rms of about 1 kHz using the standard polynomial model. The two upper vibrational states appear thus to be highly isolated except for a local perturbation of the 20012 state leading to an energy shift of 15 kHz at J = 43. A recommended list of 145 transition frequencies with kHz accuracy is obtained providing secondary frequency standards across the 1.99-2.09 µm range. The reported frequencies will be valuable to constrain the zero-pressure frequencies of the considered transitions in 12CO2 retrieval from atmospheric spectra.

CRDS with a VECSEL for broad-band high sensitivity spectroscopy in the 2.3 µm window.

The integration of an industry ready packaged Sb-based Vertical-External-Cavity Surface-Emitting-Laser (VECSEL) into a Cavity Ring Down Spectrometer (CRDS) is presented. The instrument operates in the important 2.3 µm atmospheric transparency window and provides a high sensitivity (minimum detectable absorption of 9 × 10(-11) cm(-1)) over a wide spectra range. The VECSEL performances combine a large continuous tunability over 120 cm(-1) around 4300 cm(-1) together with a powerful (∼5 mW) TEM00 diffraction limited beam and linewidth at MHz level (for 1 ms of integration time). The achieved performances are illustrated by high sensitivity recordings of the very weak absorption spectrum of water vapor in the region. The developed method gives potential access to the 2-2.7 µm range for CRDS.

Accurate measurements and temperature dependence of the water vapor self-continuum absorption in the 2.1 µm atmospheric window.

In spite of its importance for the evaluation of the Earth radiative budget, thus for climate change, very few measurements of the water vapor continuum are available in the near infrared atmospheric windows especially at temperature conditions relevant for our atmosphere. In addition, as a result of the difficulty to measure weak broadband absorption signals, the few available measurements show large disagreements. We report here accurate measurements of the water vapor self-continuum absorption in the 2.1 µm window by Optical Feedback Cavity Enhanced Absorption Spectroscopy (OF-CEAS) for two spectral points located at the low energy edge and at the center of the 2.1 µm transparency window, at 4302 and 4723 cm(-1), respectively. Self-continuum cross sections, CS, were retrieved with a few % relative uncertainty, from the quadratic dependence of the spectrum base line level measured as a function of water vapor pressure, between 0 and 16 Torr. At 296 K, the CS value at 4302 cm(-1) is found 40% higher than predicted by the MT_CKD V2.5 model, while at 4723 cm(-1), our value is 5 times larger than the MT_CKD value. On the other hand, these OF-CEAS CS values are significantly smaller than recent measurements by Fourier transform spectroscopy at room temperature. The temperature dependence of the self-continuum cross sections was also investigated for temperatures between 296 K and 323 K (23-50 °C). The derived temperature variation is found to be similar to that derived from previous Fourier transform spectrometer (FTS) measurements performed at higher temperatures, between 350 K and 472 K. The whole set of measurements spanning the 296-472 K temperature range follows a simple exponential law in 1/T with a slope close to the dissociation energy of the water dimer, D0 ≈ 1100 cm(-1).

The self- and foreign-absorption continua of water vapor by cavity ring-down spectroscopy near 2.35 µm.

The room temperature self- and foreign-continua of water vapor have been measured near 4250 cm(-1) with a newly developed high sensitivity cavity ring down spectrometer (CRDS). The typical sensitivity of the recordings is αmin≈ 6 × 10(-10) cm(-1) which is two orders of magnitude better than previous Fourier transform spectroscopy (FTS) measurements in the spectral region. The investigated spectral interval is located in the low energy range of the important 2.1 µm atmospheric transparency window. Self-continuum cross-sections, CS, were retrieved from the quadratic dependence of the spectrum base line level measured for different water vapor pressures between 0 and 15 Torr, after subtraction of the local water monomer lines contribution calculated using HITRAN2012 line parameters. The CS values were determined with 5% accuracy for four spectral points between 4249.2 and 4257.3 cm(-1). Their values of about 3.2 × 10(-23) cm(2) molecule(-1) atm(-1) are found 20% higher than predicted by the MT_CKD V2.5 model but two times weaker than reported in the literature using FTS. The foreign-continuum was evaluated by injecting various amounts of synthetic air in the CRDS cell while keeping the initial water vapor partial pressure constant. The foreign-continuum cross-section, CF, was retrieved from a linear fit of the spectrum base line level versus the air pressure. The obtained CF values are larger by a factor of 4.5 compared to the MT_CKD values and smaller by a factor of 1.7 compared to previous FTS values. As a result, for an atmosphere at room temperature with 60% relative humidity, the foreign-continuum contribution to the water continuum near 4250 cm(-1) is found to be on the same order as the self-continuum contribution.

Does the "reef structure" at the ozone transition state towards the dissociation exist? New insight from calculations and ultrasensitive spectroscopy experiments.

Since the discovery of anomalies in ozone isotope enrichment, several fundamental issues in the dynamics linked to the shape of the potential energy surface in the transition state region have been raised. The role of the reeflike structure on the minimum energy path is an intricate question previously discussed in the context of chemical experiments. In this Letter, we bring strong arguments in favor of the absence of a submerged barrier from ultrasensitive laser spectroscopy experiments combined with accurate predictions of highly excited vibrations up to nearly 95% of the dissociation threshold.

Velocity effects on the shape of pure H2O isolated lines: complementary tests of the partially correlated speed-dependent Keilson-Storer model.

Complementary tests of the partially correlated speed-dependent Keilson-Storer (pCSDKS) model for the shape of isolated transition of pure water vapor [N. H. Ngo et al., J. Chem. Phys. 136, 154310 (2012)] are made using new measurements. The latter have been recorded using a high sensitivity cavity ring down spectrometer, for seven self-broadened H(2)O lines in the 1.6 µm region at room temperature and for pressures from 0.5 to 15 Torr. Furthermore, the H(2) (18)O spectra of [M. D. De Vizia et al., Phys. Rev. A 83, 052506 (2011)] in the 1.38 µm region, measured at 273.15 K and for pressures from 0.3 to 3.75 Torr have also been used for comparison with the model. Recall that the pCSDKS model takes into account the collision-induced velocity changes, the speed dependences of the broadening and shifting coefficients as well as the partial correlation between velocity and rotational-state changes. All parameters of the model have been fixed at values previously determined, except for a scaling factor applied to the input speed-dependent line broadening. Comparisons between predictions and experiments have been made by looking at the results obtained when fitting the calculated and measured spectra by Voigt profiles. The good agreement obtained for all considered lines, at different temperature and pressure conditions, confirms the consistency and the robustness of the model. Limiting cases of the model have been then derived, showing the influence of different contributions to the line shape.

The 1.28 µm transparency window of methane (7541-7919 cm⁻¹): empirical line lists and temperature dependence (80 K-300 K).

The high sensitivity absorption spectra of methane at room temperature and 80 K were recorded by CW-Cavity Ring Down Spectroscopy in the 1.28 µm transparency window (7541-7919 cm(-1)). The empirical line parameters of 7690 and 5794 transitions were retrieved at room temperature and at 80 K, respectively. The achieved sensitivity (α(min)≈ 10(-10) cm(-1)) allowed detecting transitions with intensities as small as 5 × 10(-30) cm per molecule. In order to facilitate identification of the CH(3)D transitions present in the CRDS spectrum of methane in "natural" isotopic abundance, the spectrum of a highly enriched CH(3)D sample was recorded by differential absorption spectroscopy at room temperature and at 80 K. The CH(3)D relative contribution in the considered transparency window is found to be significant only at 80 K (up to 15%) but more limited than in the 1.58 µm transparency window.The low energy values of the transitions observed at both room temperature and 80 K were derived from the variation of their line intensities. Empirical lower states and J values have been obtained for 2821 CH(4) transitions representing 94.1 and 98.5% of the absorbance in the region at room temperature and 80 K, respectively. The good quality of these derived energy values is demonstrated by the marked propensity of the corresponding CH(4) lower state J values to be close to integers. The constructed line lists extend to higher energies the WKC (Wang-Kassi-Campargue) line lists of methane in the near infrared (1.71-1.26 µm). They allow one accounting for the temperature dependence of methane absorption between 80 K and 300 K and are of importance for the analysis of the near infrared spectrum of several planetary bodies like Titan, Uranus and Neptune. The centers of the 3ν(2) + ν(3) and 6ν(4) bands responsible of the absorption in the studied region are discussed in relation with recent theoretical calculations.

Backward supercontinuum emission from a filament generated by ultrashort laser pulses in air.

Backward emission of the supercontinuum from a light filament induced by high-intensity femtosecond laser pulses propagating in air has been observed to be enhanced compared with linear Rayleigh-Mie scattering. This enhancement is interpreted as a nonlinear scattering process onto longitudinal refractive-index changes induced by the laser pulse itself. The spectral dependence of the supercontinuum angular distribution is also investigated.

Infrared extension of the super continuum generated by femtosecond terawatt laser pulses propagating in the atmosphere.

We investigated the spectral behavior of a white-light continuum generated in air by 2-TW femtosecond laser pulses at 800 nm. The spectrum extends at least from 300 nm to 4.5 mum. From 1 to 1.6 mum the continuum's intensity increases strongly with the laser energy and depends on the initial chirp.

Frequency Agile Infrared Lidar Based on a NonTracking KNbO(3) Optical Parametric Oscillator.

We present what is to our knowledge the first mid-IR lidar system based on a KNbO(3) optical parametric oscillator pumped by a Ti:sapphire laser. The optical parametric oscillator works in a nontracking configuration and provides high-frequency agility from 1 to 4 mum. This system constitutes an extension to the IR of UV lidars described previously [Europhys. J. D 4, 231 (1998); Appl. Opt. 37, 2231 (1998); Atmos. Environ. 32, 2957 (1998)] for the determination of aerosol concentrations in urban atmospheres. As first field tests, measurements at 3.5 mum were performed in fog conditions. Water droplet size and concentration were determined from Mie calculations. Quantitative temporal mappings and angular profiles are presented.