A state-of-the-art gas electron diffraction (GED) apparatus has been reassembled in the school of chemistry at the University of Edinburgh. This combines molecularbeam and telefocus-electron-gun technologies and the alignment of the electron beam produced by the latter has been discussed. A new custom-made CCD detector has also been installed and electron diffraction patterns for a few small molecules have been recorded. In analogy to the rotating sector in a conventional GED apparatus, the new camera contains an optical filter and a procedure for its calibration is outlined and followed step by step to produce an estimate of the filter transmittance. The data have been shown to be of less than ideal quality and the probable root of the problem is discussed. GED refinements of two pairs of compounds (arachno-6,9-decaboranes, and a covalent sulfonate and thiosulfonate) are presented, using data collected with the conventional Edinburgh GED apparatus.

Gas electron diffraction (GED) is a technique that has been developed to study the molecular structure of species in the gas phase. This thesis focuses on the reconstruction of the Canterbury GED apparatus (moved from Edinburgh, UK) and the requirements for modifying the apparatus to incorporate a mass spectrometer (MS) so diffraction and MS data can be obtained within a single experiment. The combined GED-MS system has been identified in previous work in the Masters group as a necessary development for studying the structure of short-lived species generated in situ. This is particularly true for the study of ketene, which as shown in this thesis, can be generated from several precursors as part of a multiple product pyrolysis system. While GED data for ketene generated from acetic anhydride has been refined, the species formed from the pyrolysis of Meldrum’s acid were determined to be too difficult to deconvolute without additional experimental data from MS. A computational study of possible ketene derivatives that could be studied with a GED-MS apparatus is also presented. Lastly, this thesis details a structural study of the gas-phase structures of tris(chloromethyl)amine and a family of substituted disilane systems which have been determined in the gas phase for the first time. A comprehensive GED, Raman spectroscopy and ab initio study have been undertaken for tris(chloromethyl)amine [N(CH2Cl)3] which is shown to have a different structure in the solid and gas phase. Further work in the form of a molecular dynamics investigation has been identified as necessary to describe the low amplitude motion of one of the CH2Cl groups in the gas phase to allow for the GED refinement to be completed. The work on the substituted disilane systems X3SiSiXMe2 (X = F, Cl, Br, I) and X3SiSiMe3 (X = H, F, Cl, Br) demonstrates the effect of increased halogen substitution on the electronic effects of the disilanes, and the effect that the methyl groups have as larger halogens increase the steric bulk of the system.