This thesis describes the commissioning and development of a pulsed supersonic nozzle, Fourier-transform microwave spectrometer and its application to the study of several weakly bound van der Waals complexes. A pulsed supersonic expansion, Fourier-transform microwave spectrometer based on the Flygare design with a number of modifications has been constructed with an operating range of 6-18 GHz. A homodyne detection circuit mixing signals to modulus values between dc and 1 MHz is used, requiring two measurements to determine absolute transition frequencies. Transition frequencies are measured from the power spectrum by determining the first derivative zero crossing point in a least squares fitting procedure. Semiautomation of many of the spectrometer operations has been achieved allowing unattended data collection over scans of up to 300 MHz. The microwave spectrum of Ar<sub>2</sub>-OCS and Ar<sub>2</sub>-OC<sup>34</sup>S has been observed and analysed using conventional Watson S reduction hamiltonian parameters. Effective structural parameters are derived and used in a harmonic force field analysis, based on the centrifugal distortion constants, to compare the trimer interations with a model based on the sum of dimer interactions. A series of complexes containing the nitrogen molecule undergoing tunnelling motions have been studied. Hyperfine matrix elements for the first order nuclear quadrupole interaction are derived for the coupled identical nuclei case appropriate to the rapid tunnelling motions observed. The microwave spectrum of N<sub>2</sub>-OCS is described. Tunnelling and nuclear spin statistical effects for two symmetry states are observed arising from the interchange of nitrogen nuclei. Rotational and quadrupole constants are derived; an accidental near degeneracy of two rotational levels allows the off-diagonal quadrupole coupling constant to be determined from second order effects. A tunnelling hamiltonian fitting the quadrupole coupling constants to an angular potential has been used to calculate the tunnelling frequency and barrier to N<sub>2</sub> rotation. The microwave spectrum of N<sub>2</sub>-O<sub>3</sub> and a preliminary spectrum of N<sub>2</sub>-SO<sub>3</sub> have been observed. Rotation-inversion motions of the O<sub>3</sub> and SO<sub>2</sub> moieties must be considered in addition to the N<sub>2</sub> tunnelling to fit the spectrum. Tunnelling frequencies for the O<sub>3</sub>/SO<sub>2</sub> and geared motions with the N<sub>2</sub> are derived as well as structural parameters. Modifications for production of refractory molecules and complexes by laser ablation have been made. A modified nozzle employing rods of material is used with the ablation process taking place in the nozzle throat. Modifications to obtain an expansion along the axis of the microwave cavity employ a hemispherical Fabry-Perot cavity configuration. The system has been tested on a number of diatomic molecules including PbS and CuCl.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:317798 |
| Date | January 1993 |
| Creators | Connelly, James Patrick |
| Contributors | Howard, Brian J. |
| Publisher | University of Oxford |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://ora.ox.ac.uk/objects/uuid:3865eb1d-d288-44c9-8d42-84f7ff2c0608 |
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