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Title: The electronic structure of the ion pair states of molecular iodine
Author: Jewsbury, Philip J.
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1992
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The electronic configurations of molecular states of iodine are studied through the Optical-Optical Double Resonance excitation of the ion pair states in low vibrational levels. The two photon OODR excitation of ungerade IP states from the gerade ground state is rationalised and the strength of u/g coupling at the intermediate step interpreted in terms of a hyperfine interaction first described by Broyer et al. The potential function of the clg(ab) gerade coupling partner in the hyperfine Hamiltonian is derived, along with the lowest levels of a new IP state in the second cluster, H1u(2) state. An OODR excitation scheme for populating the 0-u(2) IP state is proposed and the dominant component of the c1g(ab) state configuration is found for R ≈ 5.5AA. The radiative lifetimes of nine IP states in low vibrational levels are determined and combined with the relative fluorescent intensities of the IP→Valence charge transfer transitions to derive the Einstein A-coefficients for all the strong transitions from these IP states. A theoretical model is developed in terms of a separated atom description for the electronic configurations of these states and is used to predict the relative dipole strengths of the IP→Valence transitions. The Einstein A-coefficients are then interpreted to give the electronic configurations of the IP states around R^IP_e and the relative strengths of the transition dipoles for pigma͍pigma and p _π͍pπ electron transfer between ionic centres. A significant difference from the free ion configurations is found with the lowest energy IP states of a given symmetry adopting as low a pigma occupancy at the cationic centre as the inter-electron repulsion and spin-orbit energies will allow. This stabilisation is driven by the field gradient due to the anionic charge.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available