17 research outputs found
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A kinetics and mechanistic study of the atmospherically relevant reaction between molecular chlorine and dimethyl sulfide (DMS)
A gas-phase kinetics study of the atmospherically important reaction between Cl2 and dimethyl sulfide (DMS)Cl2 + CH3SCH3 ā products has been made using a flow-tube interfaced to a photoelectron spectrometer. The rate constant for this reaction has been measured at 1.6 and 3.0 torr at T = (294 Ā± 2) K as (3.4 Ā± 0.7) Ć 10ā14 cm3 moleculeā1 sā1. Reaction (1) has been found to proceed via an intermediate, (CH3)2SCl2, to give CH3SCH2Cl and HCl as the products. The mechanism of this reaction and the structure of the intermediate were investigated using electronic structure calculations. A comparison of the mechanisms of the reactions between Cl atoms and DMS, and Cl2 and DMS has been made and the relevance of the results to atmospheric chemistry is discussed
Stability of the selfsimilar dynamics of a vortex filament
In this paper we continue our investigation about selfsimilar solutions of
the vortex filament equation, also known as the binormal flow (BF) or the
localized induction equation (LIE). Our main result is the stability of the
selfsimilar dynamics of small pertubations of a given selfsimilar solution. The
proof relies on finding precise asymptotics in space and time for the tangent
and the normal vectors of the perturbations. A main ingredient in the proof is
the control of the evolution of weighted norms for a cubic 1-D Schr\"odinger
equation, connected to the binormal flow by Hasimoto's transform.Comment: revised version, 36 page
A Study of the Alkene-Ozone reactions, ethene + O3 with Photoelectron Spectroscopy:Measurement of Product Branching Ratios and Atmospheric Implications
A Study of theĀ Alkene-Ozonereactions, 2,3-dimethyl 2-butene + O<sub>3</sub> and 2-methyl propene + O3,with Photoelectron Spectroscopy:Measurement of Product Branching Ratios and Atmospheric Implications
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A study of the atmospherically relevant reaction between molecular chlorine and dimethylsulfide (DMS): establishing the reaction intermediate and measurement of absolute photoionization cross-sections
In a study using UV photoelectron spectroscopy (PES) of the atmospherically relevant reaction CH3SCH3 + Cl-2, CH3SCH2Cl +HCl bands associated with a reaction intermediate have been observed. These have been assigned to ionization of the covalently bound molecule (CH3)(2)SCl2 on the basis of the intensity of the observed bands as a function of reaction time, molecular orbital calculations of vertical ionization energies and evidence from infrared spectroscopy. A method has also been developed, with the flow-tube/PE spectrometer combination used, to measure photoionization cross-sections of the reagents and products at the photon energy utilized and this has allowed the photoionization cross-section of the intermediate to be estimated. This work augments an earlier study in which the rate constant of the reaction between CH3SCH3 (DMS) and Cl-2 has been measured at room temperature
Multi-dimensional Limiting Process on Triangular and Tetrahedral Meshes
The present paper deals with the continuous work of extending multi-dimensional limiting process (MLP), which has been quite successfully proposed on two- and three-dimensional structured meshes, onto the unstructured meshes. The basic idea of the present limiting strategy is to control the distribution of both cell-centered and cell-vertex physical properties to mimic a multi-dimensional nature of flow physics, which can be formulated as so called the MLP condition. The MLP condition can guarantee a high order spatial accuracy without yielding spurious oscillations. Starting from the MUSCL-type reconstruction on unstructured meshes followed by the efficient implementation of the MLP condition, MLP slope limiters on unstructured meshes are proposed. Through various numerical analyses and extensive computations, it is observed that the proposed limiters are quite effective in controlling numerical oscillations and very accurate in capturing both discontinuous and continuous multi-dimensional flow features on 2-D triangular meshes and 3-D tetrahedral meshes.The authors appreciate the financial supports provided by the second stage of the Brain Korea 21 Project for
Mechanical and Aerospace Engineering Research at Seoul National University, the KARI under KHP Dual-Use
Component Development Program funded by the MKE, and by Agency for Defense Development
A modelling study of the atmospheric chemistry of DMS using the global model STOCHEM-CRI
The tropospheric chemistry of dimethylsulfide (DMS) is investigated using a global three-dimensional chemical transport model, STOCHEM with the CRIv2-R5 chemistry scheme. The tropospheric distribution of DMS and its removal at the surface by OH abstraction, OH addition, NO3 oxidation, and BrO oxidation is modelled. The study shows that the lifetime and global burden of DMS is ca. 1.2 days and 98 Gg S, respectively. Inclusion of BrO oxidation resulted in a reduction of the lifetime (1.0 day) and global burden (83 Gg S) of DMS showing that this reaction is important in the DMS budget. The percentage contribution of BrO oxidation to the total removal of DMS is found to be only 7.9% that is considered a lower limit because the study does not include an inorganic source of bromine from sea-salt. BrO oxidation contributed significantly in the high latitudes of the southern hemisphere (SH). Inclusion of DMS removal by Cl2 showed that potentially a large amount of DMS is removed via this reaction specifically in the remote SH oceans, depending on the flux of Cl2 from the Southern Ocean. Model DMS levels are evaluated against measurement data from six different sites around the globe. The model predicted the correct seasonal cycle for DMS at all locations and correlated well with measurement data for most of the periods