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Register a new userAccurate determination of the Boltzmann constant by Doppler spectroscopy: Towards a new definition of the kelvin
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Authors
Beno^it Darquie
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Accurate molecular spectroscopy in the mid-infrared region allows precision measurements of fundamental constants. For instance, measuring the linewidth of an isolated Doppler-broadened absorption line of ammonia around 10 $mu$m enables a determination of the Boltzmann constant k B. We report on our latest measurements. By fitting this lineshape to several models which include Dicke narrowing or speed-dependent collisional effects, we find that a determination of k B with an uncertainty of a few ppm is reachable. This is comparable to the best current uncertainty obtained using acoustic methods and would make a significant contribution to any new value of k B determined by the CODATA. Furthermore, having multiple independent measurements at these accuracies opens the possibility of defining the kelvin by fixing k B, an exciting prospect considering the upcoming redefinition of the International System of Units.
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In this paper, we present significant progress performed on an experiment dedicated to the determination of the Boltzmann constant, k, by accurately measuring the Doppler absorption profile of a line in a gas of ammonia at thermal equilibrium. This optical method based on the first principles of statistical mechanics is an alternative to the acoustical method which has led to the unique determination of k published by the CODATA with a relative accuracy of 1.7 ppm. We report on the first measurement of the Boltzmann constant by laser spectroscopy with a statistical uncertainty below 10 ppm, more specifically 6.4 ppm. This progress results from improvements in the detection method and in the statistical treatment of the data. In addition, we have recorded the hyperfine structure of the probed saQ(6,3) rovibrational line of ammonia by saturation spectroscopy and thus determine very precisely the induced 4.36 (2) ppm broadening of the absorption linewidth. We also show that, in our well chosen experimental conditions, saturation effects have a negligible impact on the linewidth. Finally, we draw the route to future developments for an absolute determination of with an accuracy of a few ppm.
In this paper, we present the latest results on the measurement of the Boltzmann constant kB, by laser spectroscopy of ammonia at 10 ?m. The Doppler absorption profile of a ro-vibrational line of an NH3 gas sample at thermal and pressure equilibrium is measured as accurately as possible. The absorption cell is placed inside a large 1m3 thermostat filled with an ice-water mixture, which sets the temperature very close to 273.15 K. Analysing this profile, which is related to the Maxwell-Boltzmann molecular speed distribution, leads to a determination of the Boltzmann constant via a measurement of the Doppler width (proportional tosqrt(kBT)). A spectroscopic determination of the Boltzmann constant with an uncertainty as low as 37 ppm is obtained. Recent improvements with a new passive thermostat lead to a temperature accuracy, stability and homogeneity of the absorption cell better than 1 ppm over a day.
In this paper we present an accurate analysis of the shape of an isolated rovibrational ammonia line from the strong nu2 band around 10 $mu$m, recorded by laser absorption spectroscopy. Experimental spectra obtained under controlled temperature and pressure, are confronted to various models that take into account Dicke narrowing or speed-dependent effects. Our results show clear evidence for speed-dependent broadening and shifting, which had never been demonstrated so far in NH3. Accurate lineshape parameters of the nu2 saQ(6,3) line are obtained. Our current project aiming at measuring the Boltzmann constant, kB, by laser spectroscopy will straight away benefit from such knowledge. We anticipate that a first optical determination of kB with a competitive uncertainty of a few ppm is now reachable.
The Avogadro constant links the atomic and the macroscopic properties of matter. Since the molar Planck constant is well known via the measurement of the Rydberg constant, it is also closely related to the Planck constant. In addition, its accurate determination is of paramount importance for a definition of the kilogram in terms of a fundamental constant. We describe a new approach for its determination by counting the atoms in 1 kg single-crystal spheres, which are highly enriched with the 28Si isotope. It enabled isotope dilution mass spectroscopy to determine the molar mass of the silicon crystal with unprecedented accuracy. The value obtained, 6.02214084(18) x 10^23 mol^-1, is the most accurate input datum for a new definition of the kilogram.
We report on a new optical implementation of primary gas thermometry based on laser absorption spectrometry in the near infrared. The method consists in retrieving the Doppler broadening from highly accurate observations of the line shape of the R(12) $ u_{1} + 2 u_{2}^{phantom{1}0} + u_{3}$ transition in CO$_{2}$ gas at thermodynamic equilibrium. Doppler width measurements as a function of gas temperature, ranging between the triple point of water and the gallium melting point, allowed for a spectroscopic determination of the Boltzmann constant with a relative accuracy of $sim1.6times10^{-4}$.
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