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Title: Vibrational spectra, geometry and force fields of small polyatomic molecules
Author: Mackenzie, M. W.
Awarding Body: University of Aberdeen
Current Institution: University of Aberdeen
Date of Award: 1980
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The measurement of accurate spectroscopic data has enabled determinations of molecular potential functions, molecular geometries and investigations into the effects of conformation and substitution to be performed on a variety of small polyatomic molecules. Infrared gas and polycrystalline phase studies into eight isotopically substituted species have enabled all twenty parameters of the General Harmonic Force Field (G.H.F.F.) of methyl isocyanide to be determined to within narrow limits. Comparison has been made with the predicted constants from ab initio calculations. The G.H.F.F. has then been used to determine the ground state average moments of inertia Iz, from the observed ground state rotational constants and the ground state average structure of methyl isocyanide has been subsequently derived. The effects of conformation and substitution in low molecular weight alkyl and halogeno (alkyl) germanium hydrides have been studied employing the technique of partial deuteration. The results have shown that the conclusions concerning the existence of dπ-pπ interactions drawn from previous liquid phase investigations may be suspect. Speculation has also been made on the possible existence of a distance dependent lone pair trans effect of halogen on α-hydrogens in Group IV halides. High resolution I.R. gas phase investigations of CHD2GeH3 and CH3GeHD2 have provided the A" rotational data necessary to reliably define the ground state structure of methyl germane. Similar studies of CH3GeH3 and CD3GeH3 have resulted in several reassignments being made to published data. Spectroscopic studies into eleven isotopically substituted cis and trans but-2-enes have demonstrated that the olefinic CH bond in the cis isomer is significantly stronger than that found in the trans species. Complete vibrational assignments of all available deuterated but-2-enes have been made, and these, with the help of some interaction force constants determined ab initio, have enabled high quality force fields to be calculated.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available