93 research outputs found

    Laser-based isotope ratio analyzers: the user perspective

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    Modeling the dynamic behavior of a droplet evaporation device for the delivery of isotopically calibrated low-humidity water vapor

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    A model is presented that gives a quantitative description of the dynamic behavior of a low-humidity water vapor generator in terms of water vapor concentration (humidity) and isotope ratios. The generator is based on the evaporation of a nanoliter-sized droplet produced at the end of a syringe needle by balancing the inlet water flow and the evaporation of water from the droplet surface into a dry-air stream. The humidity level is adjusted by changing the speed of the high-precision syringe pump and, if needed, the dry-air flow. The generator was developed specifically for use with laser-based water isotope analyzers in Antarctica, and it was recently described in Leroy-Dos Santos et al. (2021). Apart from operating parameters such as temperature, pressure, and water and dry-air flows, the model has as “free” input parameters: water isotope fractionation factors and the evaporation rate. We show that the experimental data constrain these parameters to physically realistic values that are in reasonable to good agreement with available literature values. With the advent of new ultraprecise isotope ratio spectrometers, the approach used here may permit the measurement of not only the evaporation rate but also the effective fractionation factors and isotopologue-dependent diffusivity ratios, in the evaporation of small droplets.</p

    High resolution optothermal spectroscopy of pyridine in the S-1 state

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    The optothermal technique has been utilized to obtain the first high resolution spectrum of pyridine in the region of the S1←S0 electronic transition. Rotational profiles for several vibronic bands (000,6a10,16b206a10,6a20,1210) were measured and found to be severely homogeneously broadened with linewidths of the order of 3–5 GHz, in agreement with previous lifetime measurements. Rotational constants of pyridine in the excited S1 vibronic levels were extracted by a band contour analysis. The values obtained are in good agreement with results from ab initio calculations, also presented here

    Probing the origins of vibrational mode specificity in intramolecular dynamics through picosecond time-resolved photoelectron imaging studies

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    We have studied the intramolecular dynamics induced by selective photoexcitation of two near-isoenergetic vibrational states in S1 p-fluorotoluene using picosecond time-resolved photoelectron imaging. We find that similar dynamics ensue following the preparation of the 13111 and 7a111 states that lie at 1990 cm-1 and 2026 cm-1, and that these dynamics are mediated by a single strongly coupled doorway state in each case. However, the lifetimes differ by a factor of three, suggesting an influence of the vibrational character of the modes involved. Our results clearly show the contribution of torsion-vibration coupling to the dynamics; this is further corroborated by comparison with the 7a111 state in S1 p-difluorobenzene, which lies at 2068 cm-1. We invoke a model in which van der Waals interactions between methyl hydrogen atoms and nearby ring carbon and hydrogen atoms leads to mixing of the vibrational and torsional states. This model predicts that enhanced torsion-vibration coupling occurs when mode 7a is excited, consistent with our observations

    Measurement of the Îœe\nu_e and Total 8^{8}B Solar Neutrino Fluxes with the Sudbury Neutrino Observatory Phase I Data Set

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    This article provides the complete description of results from the Phase I data set of the Sudbury Neutrino Observatory (SNO). The Phase I data set is based on a 0.65 kt-year exposure of heavy water to the solar 8^8B neutrino flux. Included here are details of the SNO physics and detector model, evaluations of systematic uncertainties, and estimates of backgrounds. Also discussed are SNO's approach to statistical extraction of the signals from the three neutrino reactions (charged current, neutral current, and elastic scattering) and the results of a search for a day-night asymmetry in the Îœe\nu_e flux. Under the assumption that the 8^8B spectrum is undistorted, the measurements from this phase yield a solar Îœe\nu_e flux of ϕ(Îœe)=1.76−0.05+0.05(stat.)−0.09+0.09(syst.)×106\phi(\nu_e) = 1.76^{+0.05}_{-0.05}{(stat.)}^{+0.09}_{-0.09} {(syst.)} \times 10^{6} cm−2^{-2} s−1^{-1}, and a non-Îœe\nu_e component ϕ(ΜΌτ)=3.41−0.45+0.45(stat.)−0.45+0.48(syst.)×106\phi(\nu_{\mu\tau}) = 3.41^{+0.45}_{-0.45}{(stat.)}^{+0.48}_{-0.45} {(syst.)} \times 10^{6} cm−2^{-2} s−1^{-1}. The sum of these components provides a total flux in excellent agreement with the predictions of Standard Solar Models. The day-night asymmetry in the Îœe\nu_e flux is found to be Ae=7.0±4.9(stat.)−1.2+1.3A_{e} = 7.0 \pm 4.9 \mathrm{(stat.)^{+1.3}_{-1.2}}% \mathrm{(sys.)}, when the asymmetry in the total flux is constrained to be zero.Comment: Complete (archival) version of SNO Phase I results. 78 pages, 46 figures, 34 table

    Laser spectroscopy for breath analysis : towards clinical implementation

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    Detection and analysis of volatile compounds in exhaled breath represents an attractive tool for monitoring the metabolic status of a patient and disease diagnosis, since it is non-invasive and fast. Numerous studies have already demonstrated the benefit of breath analysis in clinical settings/applications and encouraged multidisciplinary research to reveal new insights regarding the origins, pathways, and pathophysiological roles of breath components. Many breath analysis methods are currently available to help explore these directions, ranging from mass spectrometry to laser-based spectroscopy and sensor arrays. This review presents an update of the current status of optical methods, using near and mid-infrared sources, for clinical breath gas analysis over the last decade and describes recent technological developments and their applications. The review includes: tunable diode laser absorption spectroscopy, cavity ring-down spectroscopy, integrated cavity output spectroscopy, cavity-enhanced absorption spectroscopy, photoacoustic spectroscopy, quartz-enhanced photoacoustic spectroscopy, and optical frequency comb spectroscopy. A SWOT analysis (strengths, weaknesses, opportunities, and threats) is presented that describes the laser-based techniques within the clinical framework of breath research and their appealing features for clinical use.Peer reviewe
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