"December, 2003" / Includes bibliographical references (p. 311-348) / Accompanying CD-ROM entitled: 'SPM_PhD_Thesis' contains MATLAB_Algorithms (algorithms for T-ray data analysis and display, as described in the Thesis); Appendix D (Example_Raw_Data_Files - examples of raw T-ray data files, used by the MATLAB algorithms in MATLAB_Algorithms); and Thesis_PDF (a copy of the Thesis printed in Adobe's Portable Document Format (PDF)). / System requirements for accompanying CD-ROM: CD-ROM drive ; Adobe Acrobat reader ; Matlab software. / xxxiv, 358 p. : ill. (col.) ; 30 cm. + 1 CD-ROM (col. ill. ; 4 3/4 in.) / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, School of Electrical and Electronic Engineering, 2004

This thesis details research undertaken in the investigation of the open-shell open-shell Van der Waals complexes between nitric oxide (NO) and oxygen (O₂) and between nitrogen dioxide (NO₂ ) and oxygen (O</sub>2</sub> ). The Fourier transform microwave spectroscopy technique was used during the experimental work. Spectra were recorded for a mixture of NO and O₂ over the frequency range 7.0 to 18.2 GHz. Detailed ab initio calculations have been performed on the potential energy surface of both NO-O₂ and NO₂-O₂ using Multi-reference Rayleigh Schrodinger Second Order Perturbation Theory. These calculations were performed for the four distinct states of NO-O₂, ²A", ⁴A", ²A' and ⁴A', and for the two distinct states of NO,sub>2</sub>-O₂, ²A and ⁴A. Predicted rotational spectra have been generated by modelling the systems with a rigid-rotor Hamiltonians. The effective Hamiltonians included the rotational Hamiltonian, ℋ_rot, fine structure terms and hyperfine structure terms. It was not possible, for rationalizable reasons, to fit the predicted spectra for NO-O₂ to the experimental observations. Experimental details, calculation methods and rotational theory are discussed in the main body of the thesis. Predicted spectra, relevant calculations and other data is presented in the appendices.

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 Ar₂-OCS and Ar₂-OC³⁴S 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 N₂-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 N₂ rotation. The microwave spectrum of N₂-O₃ and a preliminary spectrum of N₂-SO₃ have been observed. Rotation-inversion motions of the O₃ and SO₂ moieties must be considered in addition to the N₂ tunnelling to fit the spectrum. Tunnelling frequencies for the O₃/SO₂ and geared motions with the N₂ 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.

The microwave spectrum of the open-shell van der Waals complex NO-HF has been recorded in the region 6-20GHz using a pulsed nozzle Fourier transform microwave spectrometer. This is the first observation of the microwave spectrum of a open-shell van der Waals complex between two molecules. The spectrum exhibits a rich hyperfine structure with the observation of intermolecular hyperfine interactions in an isolated system providing a sensitive probe of electron transfer in the complex. The spectrum consists of four fine structure transitions 5/2(e)-3/2(e), 3/2(e)-1/2(e), 5/2(f)-3/2(f), 3/2(f)-1/2(f) which have been fitted to a semi-rigid Hamiltonian developed to include the effects of the orbital and spin angular momenta of the unpaired electron on NO. A new treatment to account for the intermolecular hyperfine interaction was developed. The structure of the complex has been determined and is significantly bent with an angle of between 37 degrees and 49 degrees between the NO internuclear axis and the a-axis of the complex. The Renner-Teller parameter, epsilon 2, is very large and negative having the value of -10 449.32(4)GHz indicating that configuration with the unpaired electron in the plane of the complex is more stable. The analysis of the hyperfine interactions of the hydrogen and fluorine nuclei uses two constants for each nucleus, one for the spatial relationship between the magnetic moments of the unpaired electron and the nuclear magnetic moment and a Fermi-contact term. The Fermi-contact term for hydrogen is the first strong evidence of intermolecular charge transfer in an isolated van der Waals molecule.

"December, 2003" / Includes bibliographical references (p. 311-348) / Accompanying CD-ROM entitled: 'SPM_PhD_Thesis' contains MATLAB_Algorithms (algorithms for T-ray data analysis and display, as described in the Thesis); Appendix D (Example_Raw_Data_Files - examples of raw T-ray data files, used by the MATLAB algorithms in MATLAB_Algorithms); and Thesis_PDF (a copy of the Thesis printed in Adobe's Portable Document Format (PDF)). / System requirements for accompanying CD-ROM: CD-ROM drive ; Adobe Acrobat reader ; Matlab software. / xxxiv, 358 p. : ill. (col.) ; 30 cm. + 1 CD-ROM (col. ill. ; 4 3/4 in.) / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, School of Electrical and Electronic Engineering, 2004

Thesis (Ph.D.)--University of Adelaide, School of Electrical and Electronic Engineering, 2004. / "December, 2003" Includes bibliographical references (p. 311-348).

Thesis (Ph.D.)--University of Adelaide, School of Electrical and Electronic Engineering, 2005. / Includes bibliographical references (p. 349-379) and index.

Thesis (M.S.E.C.E.)--Baylor University, 2007. / Includes bibliographical references (p. 56-58).

Two aluminum spherical mirrors with radii of 203.2 mm and radii of curvature also of 203.2 mm have been used to construct a tunable Fabry-Perót type resonator operational at frequencies as low as 500 MHz. The resonator has been incorporated into a pulsed nozzle, Fourier transform, Balle-Flygare spectrometer. The spectrometer is of use in recording low J transitions of large asymmetric molecules where the spectra are often greatly simplified compared to higher frequency regions. The resonators use is illustrated by recording the rotational spectra of bromobenzene and iodobenzene. In related experiments, using similar equipment, the pure rotational spectra of four isotopomers of SrS and all three naturally occurring isotopomers of the actinide-containing compound thorium monoxide have been recorded between 6 and 26 GHz. The data have been thoroughly analyzed to produce information pertaining to bond lengths and electronic structures.

The efforts of my research have led to the successful construction of several instruments that have helped expand the field of microwave spectroscopy. The classic Balle-Flygare spectrometer has been modified to include two different sets of antenna to operate in the frequency ranges 6-18 GHz and 18-26 GHz, allowing it to function for a large range without having to break vacuum. This modified FTMW instrument houses two low noise amplifiers in the vacuum chamber to allow for the LNAs to be as close to the antenna as physically possible, improving sensitivity. A new innovative Balle-Flygare type spectrometer, the efficient low frequency FTMW, was conceived and built to operate at frequencies as low as 500 MHz through the use of highly curved mirrors. This is new for FTMW techniques that normally operate at 4 GHz or higher with only a few exceptions around 2 GHz. The chirped pulse FTMW spectrometer uses horn antennas to observe spectra that span 2 GHz versus the standard 1 MHz of a cavity technique. This instrument decreases the amount of time to obtain a large spectral region of relative correct intensity molecular transitions. A Nd:YAG laser ablation apparatus was attached to the classic Balle-Flygare and chirped pulse FTMW spectrometers. This allowed the study of heavy metal containing compounds. The instruments I constructed and the techniques I used have allowed the discovery of further insights into molecular chemistry. I have seen the effects of fluorinating an alkyl halide by determining the geometry of the carbon backbone of trans-1-iodoperfluoropropane and observing a ΔJ = 3 forbidden transition caused by a strong quadrupole coupling constant on this heavy molecule. The quadrupole coupling tensors of butyronitrile, a molecule observed in space, have been improved. The nuclear quadrupole coupling tensor of difluoroiodomethane was added to a list of variably fluorinated methyl halides upholding a trend for the magnitude of χzz. The study of SrS led to the determination of the Born-Oppenheimer breakdown terms and improving the precision of the SrS internuclear distance. I have also conducted the first pure rotational spectroscopic investigation on an actinide containing molecule, ThO.