Theoretical and experimental investigations of the Kerr Effect and Cotton-Mouton Effect.

Abstract

Mr T. J. Sono, an MSc student during the period January 2001 to January 2003, developed an apparatus to measure the pressure and temperature dependence of the electric-field induced birefringence (or electro-optic Kerr effect) in gases. Mr Sono obtained experimental results for dimethyl ether at a wavelength of 632.8 nm resulting in polarizability tensor components, first and second Kerr hyperpolarizabilities, and second Kerr-effect virial coefficients for this particular molecular species. One of the primary concerns of this thesis has been to obtain new measured Kerr-effect data for dimethyl ether and for trifluoromethane over a range of temperature. The cell has been calibrated using hydrogen as a primary standard, and has been carefully aligned to avoid multiple reflections of the incident laser beam off the closely-spaced electrode surfaces. The data has been analyzed to extract values of the polarizability anisotropy and the second Kerr hyperpolarizability for these molecules. In addition, precise values for the second Kerr-effect virial coefficients have been obtained from measurements of the Kerr effect a function of pressure. The molecular-tensor theory of the second Kerr-effect virial coefficient BK is reviewed. This theory describes the effects of intermolecular interactions on the molar Kerr constant, and it has been used to compute BK for dimethyl ether and trifluoromethane over the experimental temperature range. Agreement between experiment and theory is generally good. BK for ammonia has also been calculated, and compared to recent measured data found in the literature. The theory of the Cotton-Mouton effect (the magnetic analogue of the Kerr-effect) in a dilute gas is reviewed, and a new molecular-tensor theory describing the effects of molecular pair-interactions is developed. Calculations for a test molecule, namely chloromethane, indicate that density-dependent effects for this molecule are extremely tiny (of the order of 1% for typical experimental pressures). This new theory could be profitably used in selecting molecules which might demonstrate a larger effect which might be more readily measured in the laboratory.