Some spectroscopic studies related to atmospheric chemistry and the thermal decomposition of organic azides

Abstract

The work described in this thesis is a study of the thermal decomposition of some aliphatic azides and of the atmospherically relevant reaction between dimethyl sulphide (DMS) and molecular chlorine.  The aim of the work was to describe the mechanisms with which these reactions take place, and to identify the most important parameters influencing the reactions, such as decomposition temperature or reaction time.

UV-photoelectron spectroscopy (PES) and infrared matrix isolation spectroscopy have been used to monitor the extent of the reaction and to detect intermediates and products, and ab initio calculations have been used to facilitate spectral assignments and to provide information on the electronic structure and the thermochemistry of the reactions studied.   In the DMS + Cl₂ reaction, evidence of formation of an unstable (CH₃)₂SCl₂ species was found;  for the first time structural and spectroscopic information have been described for this reaction intermediate.

The pyrolysis of ten aliphatic azides has been studied:  two general modes of thermal decomposition were observed which were interpreted in terms of two types of reaction mechanism.  In some cases the reaction involved formation of reaction intermediates:  two of them have been observed and characterized for the first time.

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