Abstract:
During the period January 2001 to January 2003, M Sc student Mr Tleyane Jonas Sono developed an apparatus to measure the pressure- and temperature-dependence of the electro-optic Kerr effect (electric-field-induced birefringence) in gases. Mr Sono presented experimental results for dimethyl ether at a wavelength of 632.8 nm, extracting polarizability tensor components, first and second Kerr hyperpolarizabilities, and second Kerr-effect virial coefficients for this molecular species. This thesis has been primarily concerned with a thorough re-investigation of the Keneffect for the dimethyl ether molecule. Of primary concern is the reproducibility of the measured data, which depend upon precise and accurate knowledge of various experimental parameters. These include calibrations of the high-voltage power supply which is used to establish the electric field across the medium, the pressure transducer, the platinum thermistors, as well as the Faraday cell which forms the heart of the compensator. There is also a possibility of the 316-stainless-steel electrodes buckling and warping as they are cycled over ±200°C, leading to variations in the applied field and a consequent hysteresis in the results. In essence, we have been loath to publish our Kerr-effect investigation of dimethyl ether before making a thorough investigation of the reproducibility of our measured data. Here we present our investigations, and compare our new Kerr virial coefficients and the molecular (hyper)polarizability data extracted from them against the previous work of Sono. It will become apparent agreement is excellent, and that the findings for dimethyl ether are now ready for publication. The molecular-tensor theory of the Kerr-effect; including the second Kerr-effect virial coefficient BK, which describes the effects of intermolecular collisions on the molecular Kerr constant; is reviewed. The computed data is compared with the experimental data, yielding good agreement over the full experimental temperature range of 280 to 450 K. Attempts to obtain measured data at 260 K proved fruitless in the present study, though efforts are underway to complete this task.
