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Title: Exploring nonstatistical dynamic effects in exothermic organic reactions
Author: Johnson, Jamie
Awarding Body: Cardiff University
Current Institution: Cardiff University
Date of Award: 2014
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Two organic systems have been selected for the study ofnonstatistical dynamic effects using a combination of computational and lab based techniques. Chapters one and two provide an introduction to nonstatistical dynamics and computational methodology respectively. The computational element of this work focuses on the thermal rearrangements of spiropentane, and is presented in chapters three and four. The rearrangement involves two singlet biradical intermediates, and the suitability of the rearrangement to the study of nonstatistical dynamics is explored. While evidence of nonstatistical effects has been found in previous experimental work on the system, the study presented here involves molecular dynamics simulations to uncover further details about the nature and mechanism of the rearrangements. The work also involved an evaluation of the use of various density functional methods for studying the system and a benchmarking exercise to choose a suitable computational methodology for the dynamics. The results of two sets of simulations are presented, and evidence of nonstatistical effects from both is discussed. Chapters five and six concern the synthesis of a novel peroxide that was designed specifically for this work, which undergoes thermal dissociation to form a radical pair. The properties of the molecule are discussed, and various attempts at its synthesis are described. An explanation of how the compound could be used for lab-based nonstatistical dynamics studies is also presented, involving an isotopic labelling study. Unfortunately, while several synthetic routes were proposed, the synthesis was ultimately unsuccessful and so could not be used to search for nonstatistical dynamic effects.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD Chemistry