<p>The electronic structure of the ozone molecule O<sub>3</sub> has been studied with spectroscopy techniques and computations. The investigation was focused on O<sub>3</sub> in a core-hole state. The electronic configuration and the nuclear dynamics have been found to be highly correlated.</p><p>This electron correlation is mapped out for the two chemically different sites in the molecule: the central and the terminal oxygen. The energy difference between the corresponding core orbitals is 4.58 eV, which allows for site-selective core ionization and core excitation. </p><p>The influence of the core-hole site on the electronic structure is substantial, which is shown with ion and electron spectroscopy data and ab-initio quantum chemical computations. Moreover, the induced nuclear motion differs considerably for the two core-hole sites.</p><p>One of the core-excited states is proven to be ultra-fast dissociative. An analysis of the data with a formalism for two-body dissociation disclosed the localized character of core excitation. The symmetry-equivalent terminal-oxygen core orbitals do have very little overlap, so that a delocalized model for the core excitation becomes inadequate.</p><p>Moreover, core-excitation opens up a decay channel to a valence-ionized state that has not been observed with photoionization. The reason for this state to have low cross section for photoionization is illuminated with a CASSCF computation of the electronic configuration. The configuration of the state was found to be very distinct from the ground state configuration.</p><p>Another effect of configuration-interaction was found in MRCI computations of the core- ionized states. Several local minima with distinct electronic configurations could be identified.</p>
| Identifer | oai:union.ndltd.org:UPSALLA/oai:DiVA.org:uu-3914 |
| Date | January 2003 |
| Creators | Wiesner, Karoline |
| Publisher | Uppsala University, Department of Physics, Uppsala : Acta Universitatis Upsaliensis |
| Source Sets | DiVA Archive at Upsalla University |
| Language | English |
| Detected Language | English |
| Type | Doctoral thesis, comprehensive summary, text |
| Relation | Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, 1104-232X ; 921 |
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