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We report on the improved determination of the center frequency of a hydrogen deuteride vibration-rotation transition. As a result of a refined analysis of cavity ring-down absorption spectra, it was possible to quantify the influence of the hyperfine structure on the line center frequency of the weak 2-0 R(1) line, as retrieved in the Doppler-limited regime. It turns out that ignoring the hyperfine structure leads to an underestimation of the center frequency of about 350 kHz. The updated determination gives an absolute frequency of the R(1) centroid of 217 105 181.936 MHz with a global uncertainty of 76 kHz.

This paper reports the implementation of Doppler-broadening gas thermometry by use of line-shape analysis of a line-doublet. The two spectral components are vibration-rotation transitions belonging to a pair of acetylene combination bands at a wavelength of 1.39 μm. Characterized by an extraordinary spectral fidelity in combination with high resolution, the spectrometer is based on two phase-locked extended-cavity diode lasers, one of them being referenced to an optical-frequency-comb synthesizer. The global analysis of 1180 spectra, which are recorded as a function of the C2H2 pressure at the constant temperature of the triple point of water, yields an optical determination of the thermodynamic temperature with a combined relative uncertainty (type A plus type B) of 23 parts per million. Similar results are obtained at the melting point of gallium (approximately 303 K). Furthermore, we apply line-absorbance analysis to the acquired spectra, demonstrating a reduction by a factor of approximately 6 of the statistical uncertainty for the retrieved gas temperature.

Spectroscopic parameters (line intensity factor, pressure self-broadening, and shifting coefficients) of C2H2 at 1.4 μm were accurately measured using a dual-laser approach, based upon the technique of optical phase locking. This generated an absolute frequency scale underneath the absorption spectra. A pair of extended-cavity diode laserswas used. One of them, the probe laser, is forced to maintain a precise frequency offset from a reference laser, which is an optical frequency standard based on noise-immune cavity-enhanced optical heterodyne molecular spectroscopy. Laser-gas interaction takes place inside an isothermal multipass cell that is stabilized at the temperature of the triple point of water. The fidelity in the observation of the shape associated to the Pe(14) line of the 2ν3 + ν5 band allowed us to measure the spectroscopic parameters, with a global uncertainty for the line strength of 0.22%.

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We present a fully ab initio model and calculations of the spectral shapes of absorption lines in a pure molecular gas under conditions where the influences of collisions and of the Doppler effect are significant. Predictions of the time dependence of dipole autocorrelation functions (DACFs) are made for pure CO2 at room temperature using requantized classical molecular dynamics simulations. These are carried, free of any adjusted parameter, on the basis of an accurate anisotropic intermolecular potential. The Fourier-Laplace transforms of these DACFs then yield calculated spectra which are analyzed, as some measured ones, through fits using Voigt line profiles. Comparisons between theory and various experiments not only show that the main line-shape parameters (Lorentz pressure-broadening coefficients) are accurately predicted, but that subtle observed non-Voigt features are also quantitatively reproduced by the model. These successes open renewed perspectives for the understanding of the mechanisms involved (translational-velocity and rotational-state changes and their dependences on the molecular speed) and the quantification of their respective contributions. The proposed model should also be of great help for the test of widely used empirical line-shape models and, if needed, the construction of more physically based ones.

We report on a new implementation of Doppler broadening thermometry based on precision absorption spectroscopy by means of a pair of offset-frequency locked extended-cavity diode lasers at 1:39 m. The method consists in the highly accurate observation of the shape of the 44;1 ! 44;0 line of the H2 18O 1 þ3 band, in a water vapor sample at thermodynamic equilibrium. A sophisticated and extremely refined spectral analysis procedure is adopted for the retrieval of the Doppler width as a function of the gas pressure, taking into account the Dicke narrowing effect, the speed dependence of relaxation rates, and the physical correlation between velocity-changing and dephasing collisions. A spectroscopic determination of the Boltzmann constant with a combined (type A and type B) uncertainty of 24 parts over 106 is reported. This is the best result obtained so far by means of an optical method. Our determination is in agreement with the recommended CODATA value.

A laser absorption technique, based upon a pair of offset-frequency-locked extended-cavity diode lasers, was employed to perform line-shape measurements for H218O vibration-rotation transitions at 1.38 μm, with an extremely high spectral fidelity. This important feature was mostly ensured by the highly accurate, absolute, and repeatable frequency axis characterizing each acquired spectrum. We present the outcomes of a specific study of the speed dependence of collision parameters influencing the shape of the H218O absorption lines. More particularly, the performance of the quadratic approximation, either used alone or considered in conjunction with the Dicke narrowing effect, was investigated and compared to that of the confluent hypergeometric dependence. Hence, experimental evidences of the partial failure of the quadratic approximation are given and discussed. Finally, we investigate the possible influence of the choice of the speed-dependent line-shape model on the retrieved collisional parameters.

Very recently, a spectroscopic determination of the Boltzmann constant, kB, has been performed at the Second University of Naples by means of a rather sophisticated implementation of Doppler Broadening Thermometry (DBT)1. Performedon a 18O-enriched water sample, at a wavelength of 1.39 µm, the experiment has provided a value for kB with a combined uncertainty of 24 parts over 106, which is the best result obtained so far, by using an optical method.In the spectral analysis procedure, the partially correlated speed-dependent hard-collision (pC-SDHC) model was adopted. The uncertainty budget has clearly revealed that the major contributions come from the statistical uncertainty (type A) and from the uncertainty associated to the line-shape model (type B)2. In the present work, we present the first results of a theoretical and numerical work aimed at reducing these uncertainty components. It is well known that molecular line shapes exhibit clear deviations from the time honoured Voigt profile. Even in the case of a well isolated spectral line, under the influence of binary collisions, in the Doppler regime, the shape can be quite complicated by the joint occurrence of velocity-change collisions and speed-dependent effects. The partially correlated speed-dependent Keilson-Storer profile (pC-SDKS) has been recently proposed as a very realistic model, capable of reproducing very accurately the absorption spectra for self-colliding water molecules, in the near infrared3. Unfortunately, the model is so complex that it cannot be implemented into a fitting routine for the analysis of experimental spectra. Therefore, we have developed a MATLAB code to simulatea variety of H218O spectrain thermodynamic conditions identical to the one of our DBT experiment, using the pC-SDKS model. The numerical calculations to determine such a profile have a very large computational cost, resulting from a very sophisticated iterative procedure. Hence, the numerically simulated spectra (with the addition of random noise) have been used to test the validity of simplified line shape models, such as the speed-dependent Galatry (SDG) profile and pC-SDHC model. In particular, we have used the global fitting procedure that is described in Amodio et al4. Such a procedure is very effective in reducing the uncertainty resulting from statistical correlation among free parameters. Therefore, the analysis of large amounts of simulated spectra has allowed us to study the influence of the choice of the model and quantify the achievable precision and accuracy levels, at the present value of the signal-to-noise ratio.

We present the outcomes of a specific study on the quadratic approximation in the partially-Correlated Speed-Dependent Hard-Collision profile (pC-SDHC), which is currently the recommended profile to replace the Voigt convolution for the shape of isolated high-resolution rotational-vibrational transitions, when perturbed by neutral gas-phase molecules. It includes the main effects occurring in the line formation, in particular the Dicke narrowing and the speed-dependent effects, as well as the possible correlation between them. We tested the quadratic (q-) and hypergeometric (hg-) versions for the speed dependence of the pC-SDHC on high quality H218O absorption spectra, in coincidence with three vibration-rotation transitions of the ν1 + ν3 band, at 1.39µm, looking for possible differences in the retrieved parameters. The absorption spectra were observed in the Doppler regime, with unprecedented spectral fidelity, by using a dual-laser absorption spectrometer, recently developed for the aim of a spectroscopic determination of the Boltzmann constant. The investigated transitions were: 22,1 → 22,0 , 44,1 → 44,0 and 30,3 → 20,2. The pC-SDHC profile is found to be quite robust, regardless of the choice of the particular speed dependence, provided that the velocity-changing collision frequency is considered as a free parameter. In particular, the pressure broadening and shifting parameters, retrieved by using the quadratic and hypergeometric versions, were found to be fully consistent. Similarly, the integrated absorbance was found to be completely unaffected by the choice of the speed-dependence, in the whole pressure range that we have explored. It should be said, however, that the velocity-changing collision frequency resulted to be physically meaningful only for the hg-version, but not for the q-version. Therefore, in the quadratic approximation, the collision frequency must be considered just as an indispensable parameter to be included in the fitting procedure for the aims of a successful fit.