Non-reactive scattering of rotational quantum state selected molecular beams
Degree GrantorUniversity of Canterbury
Degree NameDoctor of Philosophy
Non-reactive scattering of rotational quantum state selected molecular beams of symmetric top molecules has been investigated using electrostatic methods. Cross-sections for the defocusing of upper Stark-state molecules in a hexapole electric field have been measured for neat and seeded beams of CH3F with a range of polar and non-polar quencher gases. Calculations of the hexapole focusing voltages for specific rotational states facilitated the assignment of the defocusing cross-sections to individual rotational states in the beam. The technique of Molecular Beam Electric Resonance (MBER) spectrometry has been employed to detect and study individual rotational states, resulting in a dramatic improvement in quantum state resolution over the use of a single hexapole filter. Cross-sections have been measured for the relaxation of selected upper Stark states in beams of methyl halides with a range of polar and non-polar scattering gases. The application of MBER spectrometry to rotational state identification in beams of symmetric to molecules has been explored in this study. Information on the velocity, temperature, and rotational state distribution of the beam can be easily obtained from experimentation using this arrangement. It has also provided insight into the focusing properties of hexapole electric filters. Individual rotational quantum states in a beam of symmetric top molecules could be tagged using an MBER spectrometer for studies of rotational state dependent properties, such as the effect of rotational states in scattering studies. The collisional relaxation of upper Stark-state molecules in a beam could occur through several mechanisms. Cross-sections measured using the technique of MBER have been largely attributed to an Mᴊ changing process. The effects of the long-range attractive van der Waals interaction potential, the relative velocity dependence of the collision partners and the electric field dependence of the Stark energy have been considered in order to account for the magnitude of the relaxation cross-sections measured in this study.