Abstract:The report of an IUPAC Task Group, formed in 2011 on "Intensities and line shapes in high-resolution spectra of water isotopologues from experiment and theory" (Project No. 2011-022-2-100), on line profiles of isolated high-resolution rotational-vibrational transitions perturbed by neutral gas-phase molecules is presented. The well-documented inadequacies of the Voigt profile (VP), used almost universally by databases and radiative-transfer codes, to represent pressure effects and Doppler broadening in isolated vibrationalrotational and pure rotational transitions of the water molecule have resulted in the development of a variety of alternative line-profile models. These models capture more of the physics of the influence of pressure on line shapes but, in general, at the price of greater complexity. The Task Group recommends that the partially Correlated quadratic-Speed-Dependent Hard-Collision profile (pCqSD-HCP) should be adopted as the appropriate model for high-resolution spectroscopy. For simplicity this should be called the Hartmann-Tran profile (HTP). The HTP is sophisticated enough to capture the various collisional contributions to the isolated line shape, can be computed in a straightforward and rapid manner, and reduces to simpler profiles, including the Voigt profile, under certain simplifying assumptions.

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  μm. The method consists in the highly accurate observation of the shape of the 4(4,1)→4(4,0) line of the H2(18)O ν1+ν3 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 10(6) 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.

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We present extensive molecular dynamics simulations on species segregation in a granular mixture subject to vertical taps. We discuss how grain properties, e.g., size, density, friction, as well as shaking properties, e.g., amplitude and frequency, affect such a phenomenon. Both the Brazil nut effect (larger particles on the top, BN) and the reverse Brazil nut effect (larger particles on the bottom, RBN) are found and we derive the system comprehensive "segregation diagram" and the BN to RBN crossover line. We also discuss the role of friction and show that particles which differ only for their frictional properties segregate in states depending on the tapping acceleration and frequency.