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A spectroscopic study on some atmospherically relevant reactions with the support of electronic structure calculations

A spectroscopic study on some atmospherically relevant reactions with the support of electronic structure calculations
A spectroscopic study on some atmospherically relevant reactions with the support of electronic structure calculations
The work described in this thesis is a study of the atmospherically relevant reactions of
dimethyl sulfide (DMS) with halogen and interhalogen molecules (Cl2, Br2, I2, BrCl and
ICl) and ozone with selected alkenes (ethylene, tetramethylethylene and 2-methylpropene).
The aim was to investigate the mechanisms of these reactions and identify reaction inter-
mediates.

Infrared matrix isolation spectroscopy and u.v.-photoelectron spectroscopy were used to
detect intermediates and products, and ab initio calculations were used to facilitate spec-
tral assignments and to provide information on the structure of the molecules studied.
The results confirm and extend previous matrix isolation infrared studies on the DMS/Cl2
system and also provide vibrational assignment and ab initio calculations for the electronic
structure of the intermediates present in the related DMS/Br2, DMS/I2, DMS/BrCl and
DMS/ICl reactions. For all systems, the intermediate is shown to be a van der Waals
complex of the type DMS:XY, where XY is a halogen or interhalogen molecule.

The reactions of ozone and alkenes were studied by u.v.-photoelectron spectroscopy. The
results follow the general mechanism proposed by Criegee but no Criege intermediate is
observed. Reaction mechanisms are presented and discussed for each reaction investi-
gated.

Of great importance is the observation of the first excited state of oxygen (O2 a1 ? g) in
the reactions of ozone with ethylene and 2-methylpropene which play an important role
in the oxidation chemistry of the troposphere.
Beccaceci, Sonya
379c1164-a987-4fc7-94ff-12646acdb02e
Beccaceci, Sonya
379c1164-a987-4fc7-94ff-12646acdb02e
Dyke, John
46393b45-6694-46f3-af20-d7369d26199f

Beccaceci, Sonya (2010) A spectroscopic study on some atmospherically relevant reactions with the support of electronic structure calculations. University of Southampton, School of Chemistry, Masters Thesis, 113pp.

Record type: Thesis (Masters)

Abstract

The work described in this thesis is a study of the atmospherically relevant reactions of
dimethyl sulfide (DMS) with halogen and interhalogen molecules (Cl2, Br2, I2, BrCl and
ICl) and ozone with selected alkenes (ethylene, tetramethylethylene and 2-methylpropene).
The aim was to investigate the mechanisms of these reactions and identify reaction inter-
mediates.

Infrared matrix isolation spectroscopy and u.v.-photoelectron spectroscopy were used to
detect intermediates and products, and ab initio calculations were used to facilitate spec-
tral assignments and to provide information on the structure of the molecules studied.
The results confirm and extend previous matrix isolation infrared studies on the DMS/Cl2
system and also provide vibrational assignment and ab initio calculations for the electronic
structure of the intermediates present in the related DMS/Br2, DMS/I2, DMS/BrCl and
DMS/ICl reactions. For all systems, the intermediate is shown to be a van der Waals
complex of the type DMS:XY, where XY is a halogen or interhalogen molecule.

The reactions of ozone and alkenes were studied by u.v.-photoelectron spectroscopy. The
results follow the general mechanism proposed by Criegee but no Criege intermediate is
observed. Reaction mechanisms are presented and discussed for each reaction investi-
gated.

Of great importance is the observation of the first excited state of oxygen (O2 a1 ? g) in
the reactions of ozone with ethylene and 2-methylpropene which play an important role
in the oxidation chemistry of the troposphere.

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Published date: February 2010
Organisations: University of Southampton

Identifiers

Local EPrints ID: 171159
URI: https://eprints.soton.ac.uk/id/eprint/171159
PURE UUID: db270293-173c-4528-b33e-ae84e5cbb378
ORCID for John Dyke: ORCID iD orcid.org/0000-0002-9808-303X

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Date deposited: 08 Feb 2011 10:11
Last modified: 06 Jun 2018 13:17

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