Investigation of Atmospheric Chemical Mechanisms Using Experiments and Theory

This thesis IS divided into two parts. Part I provides a detailed discussion of the design ami construction of a highly instrumented reactor for atmospheric chemistry (HlRAC). The main analytical tool'constraining HlRAC's design is its multipass FTIR absorption spectroscopy optical system. Apart from the FTIR system, HIRAC features an extensive suite of instrumentation en'abling simultaneous measurement of several different atmospheric trace gases. This capability allows experimental flexibility, and potentially provides multiple constraints in the development and testing of atmospheric oxidation mechanisms. The initial experimental results obtained from the system show HlRAC's capacity to facilitate atmospheric chemistry research at Leeds, linking laboratory and theoretical investigations of elementary reactions with VOC mechanism development. Part II discusses theoretical work conducted in order to -explore reaction kinetics and product yields of elementary reactions that are significant to the chemistry of planetary atmospheres. The tools for theoretical analysis include: (1) electronic structure theory, (2) statistical theories for describing reaction rates and product energy partitioning, (3) the energy grained master equation (EGME), and (4) trajectory simulations. In conjuction with experimental data, .these techniques permit a detailed' understanding of reaction mechanisms under a range of conditions that are relevant to the chemistry of planetary atmospheres. They also facilitate experimental design in: (1) laboratory studies of elementary reactions and (2) chamber studies of more complex oxidation systems, such as may be carried out in HIRAC.EThOS - Electronic Theses Online ServiceGBUnited Kingdo