A study of the atmospherically relevant reaction between molecular chlorine and dimethylsulfide (DMS): establishing the reaction intermediate and measurement of absolute photoionization cross-sections
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.
atmospheric chemistry, reactive intermediate, photoionization, cross-sections, dimethyl sulfide reaction matrix-isolation, dihalogenodimethylselenium compounds, sulfur, sulfide, spectroscopy, atoms, complexes, halogen, bases, cl-2
85-95
Dyke, J.M.
46393b45-6694-46f3-af20-d7369d26199f
Ghosh, M.V.
210ab8df-8389-4bf5-9622-9931cc4a9f81
Goubet, M.
63668b91-2217-416f-ba9d-e00a68f22e9f
Lee, E.P.F.
f47c6d5d-2d1f-4f03-a3ff-03658812d80b
Levita, G.
ef218c00-047c-4ec3-a056-b78237ca2e94
Miqueu, K.
ec42f84e-a56f-438c-b8da-5970a86258c0
Shallcross, D.E.
9b36ee5a-feb1-4fea-a34c-f56e64dfae28
9 May 2006
Dyke, J.M.
46393b45-6694-46f3-af20-d7369d26199f
Ghosh, M.V.
210ab8df-8389-4bf5-9622-9931cc4a9f81
Goubet, M.
63668b91-2217-416f-ba9d-e00a68f22e9f
Lee, E.P.F.
f47c6d5d-2d1f-4f03-a3ff-03658812d80b
Levita, G.
ef218c00-047c-4ec3-a056-b78237ca2e94
Miqueu, K.
ec42f84e-a56f-438c-b8da-5970a86258c0
Shallcross, D.E.
9b36ee5a-feb1-4fea-a34c-f56e64dfae28
Dyke, J.M., Ghosh, M.V., Goubet, M., Lee, E.P.F., Levita, G., Miqueu, K. and Shallcross, D.E.
(2006)
A study of the atmospherically relevant reaction between molecular chlorine and dimethylsulfide (DMS): establishing the reaction intermediate and measurement of absolute photoionization cross-sections.
Chemical Physics, 324 (1), .
(doi:10.1016/j.chemphys.2005.11.045).
Abstract
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.
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Published date: 9 May 2006
Keywords:
atmospheric chemistry, reactive intermediate, photoionization, cross-sections, dimethyl sulfide reaction matrix-isolation, dihalogenodimethylselenium compounds, sulfur, sulfide, spectroscopy, atoms, complexes, halogen, bases, cl-2
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Local EPrints ID: 44428
URI: http://eprints.soton.ac.uk/id/eprint/44428
PURE UUID: 4368d054-5264-4f5d-85f6-7d6fb370f78a
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Date deposited: 01 Mar 2007
Last modified: 16 Mar 2024 02:36
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Contributors
Author:
M.V. Ghosh
Author:
M. Goubet
Author:
E.P.F. Lee
Author:
G. Levita
Author:
K. Miqueu
Author:
D.E. Shallcross
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