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1.
Phys Chem Chem Phys ; 13(45): 20326-34, 2011 Dec 07.
Artículo en Inglés | MEDLINE | ID: mdl-21993923

RESUMEN

The case of symmetric tops CH(3)X (X = Br, Cl, F, …) perturbed by non-polar diatoms Y(2) (Y = N(2), O(2), …) is analysed from the viewpoint of theoretical collisional broadening of their rotational lines observed in atmospheric spectra. A semi-classical approach involving an exponential representation of the scattering operator and exact trajectories governed by the isotropic potential is presented. For the first time the active molecule is strictly treated as a symmetric top and the atom-atom interactions are included in the intermolecular potential model. It is shown for the CH(3)Cl-O(2) system that these interactions contribute significantly to the line width for all values of the rotational quantum numbers J and K. Additional testing of modifications required in the semi-classical formalism for a correct application of the cumulant expansion is performed and it is shown that the use of the cumulant average on the rotational states of the perturbing molecule leads to entirely negligible effects for the not very strongly interacting CH(3)Cl-O(2) system. In order to check the theoretical predictions and to extend the scarce experimental data available in the literature to higher values of the rotational quantum numbers, new measurements of room-temperature O(2)-broadened CH(3)Cl rotational lines are carried out by a photomixing continuous-wave terahertz spectrometer. The experimental line widths extracted with a Voigt profile model demonstrate an excellent agreement with theoretical results up to very high J-values (J = 31, 37, 40, 45, 50).

2.
Rev Sci Instrum ; 82(3): 034102, 2011 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-21456766

RESUMEN

Preparation of high purity ozone as well as precise and accurate measurement of its pressure are metrological requirements that are difficult to meet due to ozone decomposition occurring in pressure sensors. The most stable and precise transducer heads are heated and, therefore, prone to accelerated ozone decomposition, limiting measurement accuracy and compromising purity. Here, we describe a vacuum system and a method for ozone production, suitable to accurately determine the pressure of pure ozone by avoiding the problem of decomposition. We use an inert gas in a particularly designed buffer volume and can thus achieve high measurement accuracy and negligible degradation of ozone with purities of 99.8% or better. The high degree of purity is ensured by comprehensive compositional analyses of ozone samples. The method may also be applied to other reactive gases.

3.
Opt Lett ; 30(24): 3320-2, 2005 Dec 15.
Artículo en Inglés | MEDLINE | ID: mdl-16389818

RESUMEN

We demonstrate a new, simple technique for measuring IR frequencies near 30 THz by using a femtosecond (fs) laser optical comb and sum-frequency generation. The optical frequency is directly compared with the distance between two modes of the fs laser, and the resultant beat note is used to control this distance, which depends only on the repetition rate of the fs laser. The absolute frequency of a CO2 laser stabilized onto a SF6 two-photon line has been measured for the first time to the authors' knowledge. This line is an attractive alternative to the usual saturated absorption OsO4 resonances used for the stabilization of CO2 lasers. First results demonstrate a fractional Allan deviation of 3 x 10(-14) at 1 s.

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