The binary complexes comprising the molecules hydrogen fluoride, hydrogen chloride, water, hydrogen sulphide, ammonia, phosphine, methane and silane have been studied by ab initio molecular orbital theory thus generating a matrix of eight by eight molecular complexes. The structures, energetics and vibrational spectra of these molecular complexes, both homodimers and heterodimers, have been studied at the second order level of Møller-Plesset perturbation theory using the 6-31G** basis set, by means of the Gaussian 92 computer program. The self consistent field interaction energies have been further dissected into their various components according to the Morokuma scheme, using the Monstergauss computer program. An analysis of the computed interaction energies of the complexes has also been carried out. A complete normal mode analysis, identifying the normal modes of Vibration, has been carried out using the Vibra program. The infrared spectra of some of the associated species have also been determined experimentally by means of the matrix isolation technique using argon and nitrogen as matrix gases. The combined use of the theoretical and experimental approaches has enabled reliable vibrational assignments to be made, which have been used in determining the molecular structures of the aggregates formed on complexation. / Thesis (Ph.D.)-University of Natal, Durban, 1999.

2-Cyanoethyldiphenylphosphine (L) was synthesized from diphenylphosphine and acrylonitrile using an aqueous base as a catalyst. This ligand reacted with Pt(II) and Pd(II) salts to yield complexes of the stoichioretry MX2L2 (X = Cl, Br, NCS). In these complexes the ligand was found to function as a monodentate phosphine. infrared spectroscopic evidence suggested that the platinum complexes are of cis and the palladium complexes of trans geometries.A complex of the stoichiometry Pd2Cl4L2 was isolated from a 1:1. mole ratio of PdCl2 to L. Spectroscopic evidence suggested that the complex is a ligand bridged dieter which utilizes the phosphorus and nitrogen lone pairs of L. The nitrile groups in this complex reacted rapidly with alcohols to yield coordinated imino-ether groups.

The interaction between sunlight and our atmosphere is one of the most fundamental processes affecting weather and climate. The majority of the Sun�s radiation is produced in the ultraviolet, visible and near-infrared regions of the electromagnetic spectrum. These spectral regions correspond to the energies of vibrational overtone and electronic transitions. The composition of our atmosphere is complex, and many trace species have a large influence on its chemistry and dynamics. Hydrogen bound hydrated complexes are trace species that could play an important role in the Earth�s atmosphere. However, before this role can be quantified, spectral identification and characterisation of these complexes is essential. We have developed vibrational local mode Hamiltonians to simulate the absorption spectra of hydrated complexes. To test the approximations made in the vibrational model, we have peformed calculations on the diatomics OH, HF and CO, which can be considered to act as pure local modes. When highly correlated ab initio methods and large basis sets are used to calculate the potential energy and dipole moment curve, the simulated vibrational transitions of the diatomics are in excellent agreement with experiment. We have derived approximate vibrational Hamiltonians which describe the OH-stretching and HOH-bending modes of vibration in the complexes H₂O�H₂O, H₂O�HO₂ and H₂O�HO. The calculated spectrum of H₂O�H₂O has been used to assess its atmospheric importance, and to succesfully guide experimental efforts to detect H₂O�H₂O in the laboratory and the Earth�s atmosphere. The calculated transition energies and intensities of H₂O�H₂O and H₂O�HO are in good agreement with experimental matrix isolation and gas-phase studies. To investigate the effect of low frequency modes on OH-stretching overtone spectra we have simulated the spectrum of HOONO. We have derived a Hamiltonian that couples the NOOH-torsional mode to the high frequency OH-stretching and OOH-bending modes. The simulated spectrum is in good agreement with the experimentally observed spectrum. We find that the OH-stretching spectra are perturbed strongly only if the barrier to torsion is low. We have also investigated changes in the electronic spectrum of hydrated complexes and the corresponding parent monomers. Upon complex formation, the lowest-lying electronic transition in the hydroxyl radical is strongly redshifted outside the region of monomeric absorption.

Bibliography: leaves 230-242 / 242 leaves : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, 1986

Typescript / Includes bibliographical references / 250 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1967

ii, 137 leaves : ill., graphs, tables ; 31 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1980

75 leaves : graphs ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.1980) from the Dept. of Physical and Inorganic Chemistry, University of Adelaide

Thesis (Ph.D. 1980) from the Department of Physical and Inorganic Chemistry, University of Adelaide.

Thesis (Ph.D.) -- University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1980.

Thesis (Ph.D.) -- University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1967. / [Typescript]. Includes bibliographical references.