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Title: Fourier transform infrared spectroscopic and structural studies of small molecules
Author: Harper, J.
Awarding Body: University of Aberdeen
Current Institution: University of Aberdeen
Date of Award: 1984
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The work described in this thesis is principally concerned with the analyses at high resolution (∼ 0.05 cm-1) of the infrared gas phase bands of symmetric and asymmetric top molecules. The species studied are isotopic forms of ethane, ethylene and diborane. In the case of diborane the derived rotation, vibration and vibration - rotation constants have been further used to determine an accurate harmonic potential function and the precise molecular structure. Complete analyses have been performed for the nu2, nu 9, nu11 and nu2 fundamentals of CH3CD 3 and 13CH3CD3. Sets of upper state parameters are determined along with an estimate of the ground state centrifugal distortion constant, DK, for each isotopic species. Perturbations in the nu9 band are accounted for in terms of an A1 - E Coriolis interaction with nu3 and in the nu11 band in terms of the combined effects of an A1 - E Coriolis interaction with nu4 and an E(+/- z) ↔ E (= z) interaction with nu10. A small, localised perturbation in is identified as due to higher order rotational resonance with 2nu92. All first and second order Coriolis interaction parameters are determined. High resolution infrared studies of isotopic ethylenes have been undertaken in the region below 2000 cm-1. Accurate vibration and rotation parameters for the fundamentals of C2H4 and C2 D4 are determined. A full upper state rovibration analysis of the nu7 fundamental of C2D4 is achieved, once the various effects of indirect Coriolis interaction with the inactive nu 4 torsion vibration are taken into account. Several localised perturbations are identified and from these the band centre of the inactive nu4 vibration is estimated accurately. Complete analyses of the nu2, nu 12, 2nu7 and 2nu8 bands of H2CCd 2 reported. Localised perturbations are identified and taken into account in the analyses, enabling the perturbing vibrational levels to be located accurately and the interaction parameters to be determined. Ground state rotation and quartic distortion constants are obtained for 11B2H6 and 11B2D6 from the analyses of the nu17 and nu18 type-A and nu14 and nu9 + nu15 type-C bands of 11B2D6 . Sets of upper state parameters are determined for all vibration levels studied and several localised perturbations are observed and identified. The data obtained from these and previous spectroscopic studies of diborane allow a precise determination of the empirical harmonic potential function to be made for the first time. Thirty of the thirty three independent force constants are determined with numerical significance. The physical significance of the values is probably best demonstrated by the close agreement throughout with scaled ab initio force constants from two independent sources. Finally the availability from this and previous work of 12 precisely determined ground state spectroscopic rotation constants for isotopic diboranes, and a physically realistic harmonic potential function, enables the ground state ro substitution rs, zero-point average r z, and equilibrium r structures to be calculated. The rz and re parameters are entirely compatible with, but more accurately determined than, those available from electron diffraction studies.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Atomic physics & molecular physics Atoms Molecules