This thesis presents a joint experimental and theoretical study of a bimolecular collision between OH(A) and H<sub>2</sub> diatoms. The study focuses on the relationship between the initial, <b><i>j</i></b>, and final rotational angular momentum, <b><i>j'</i></b>. This relationship is explored from both a scalar point of view by measuring rotational energy transfer (RET), and a vectorial viewpoint by considering the collisional depolarisation. The experimental technique used in this investigation, Zeeman quantum beat spectroscopy, is first demonstrated by applying it to the determination of the lab-frame orientation of OH(X) photofragments following the photolysis of H<sub>2</sub>O<sub>2</sub>. The H<sub>2</sub>O<sub>2</sub> is photolysed by circularly-polarised light at 248 nm, and Zeeman quantum beat spectroscopy probes the angular momentum orientation as a function of the photofragment spin-rotation level. The results of this experiment are compared with orientation parameters predicted by a simulation that couples the rotation of the parent molecule to the torsional motion during bond cleavage. The calculations from the model agree qualitatively with those from the experiment. The Zeeman quantum beat spectroscopy technique is then used to monitor the evolution of angular momentum polarisation of OH(A) radicals during collisions with H<sub>2</sub>. The technique allows for the determination of depolarisation cross sections for oriented and aligned distributions, as a result of collisions with H<sub>2</sub>. Alongside this, cross sections for collisional quenching to non-reactive OH(X)+H<sub>2</sub> and reactive H<sub>2</sub>O+H products are determined. By resolving the fuorescence with a monochromator the contributions to depolarisation from elastic collisions (the elastic depolarisation cross sections) are measured alongside cross sections for RET. Cross sections for total depolarisation and rotational energy transfer demonstrate only weak dependence on the rotational quantum number of the OH(A) radical, <i>N</i><sub>OH</sub>. Competing quenching processes that fall with <i>N</i><sub>OH</sub> are likely a considerable cause of this weak dependence. Furthermore, the polarisation of the angular momentum of OH(A) is randomised following RET. The elastic depolarisation cross sections make only a small contribution to the depolarisation and fall with increasing <i>N</i><sub>OH</sub>. Collectively these trends have not been seen previously in similar studies on OH(A) collisions with atomic colliders. For the theoretical calculations, a four-atom quasi-classical trajectory (QCT) method has been developed, utilising Lagrangian multipliers to fix the OH(A) and H<sub>2</sub> bonds. The calculations demonstrate that collisions involving the formation of complexes that survive for several rotational periods are prevalent in this collision system, and that these lead to large amounts of depolarisation. The calculations also demonstrate that RET in the H<sub>2</sub> diatom supports higher levels of RET in OH(A) than seen in previous triatomic systems. Additionally, when one diatom is depolarised the accompanying diatom is typically also depolarised. These trends, at least in part, are owed to the highly attractive and anisotropic potential energy surface (PES) describing the interaction. The QCT calculations overestimate the experimentally-measured cross sections by more than a factor of 2. The calculations are adiabatic and do not account for the non-adiabatic activity associated with this collision system, and this is likely one cause of the discrepancies. In an attempt to further account for this overestimation, alternative angular momentum binning approaches for the QCT calculations are developed, but with limited success. Further exploration of the topology of the PES used in the calculations suggests that inadequacies in this surface are a major contributor to the discrepancies.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:680412 |
| Date | January 2015 |
| Creators | Seamons, Scott Andrew |
| Contributors | Brouard, Mark |
| Publisher | University of Oxford |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://ora.ox.ac.uk/objects/uuid:36319557-1efa-4840-8f46-c15479945a0c |
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