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Title: Rydberg ionisation into confined and discrete systems
Author: Gibbard, Jemma
ISNI:       0000 0004 5366 0774
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2015
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The energy levels of a hydrogen Rydberg atom approaching a metallic structure are perturbed by the image-charge interaction with the surface. At small atom-surface separations surface ionisation of the Rydberg electron can occur, whereby the electron is transferred to a metal-localised state. In previous studies investigating surface ionisation at bulk metallic surfaces, this state has been part of a conduction band; however this thesis focuses on metallic and structured surfaces where the Rydberg electron transfers into a discrete image-state or hybrid 'well-image state'. The surface ionisation of hydrogen Rydberg atoms at a Cu(100) projected band-gap surface is investigated experimentally and theoretically. Experimentally, the surface ionisation of an incident beam of hydrogen Rydberg atoms is measured by extraction of the resulting ions. Resonance-enhanced charge transfer is seen for hydrogen Rydberg states that are degenerate with copper-localised image-states. A wavepacket propagation study shows that for on-resonance states the maximum in the surface-ionisation probability is shifted away from the surface by decreasing the collisional velocity. The discrete hybrid 'well-image states' localised along the surface normal of a thin-film change energy with thin-film thickness. The interaction of hydrogen Rydberg atoms with iron thin films deposited on an insulating substrate is investigated. The preference for electron penetration along the surface normal is seen by the resonance-enhancement of charge transfer at energies where the Rydberg state and well-image state are degenerate. By changing the thickness of the thin film, by in situ depositions, the energies of the well-image state are altered and the Rydberg n-values at which resonances occur, change. At a thickness of 30-monolayer the energetic spacings between the well-image states and the Rydberg states become comparable, and the single well-image state resolution is lost. A wavepacket-propagation study investigates the interaction of a nanoparticle and low-n hydrogen Rydberg atoms. The nanoparticle has a fully confined potential which at small radii yields well-spaced, fully discrete well-image states. Resonance-enhanced charge transfer occurs when the Rydberg state and the nanoparticle well-image state energy levels are degenerate. However, when there is poor energy matching between the nanoparticle well-image state and the Rydberg atom, no charge transfer is seen i.e. surface ionisation does not occur. Overall, the work presented here demonstrates the capability of Rydberg-surface studies to identify discrete, high-lying energy levels at specific surfaces.
Supervisor: Softley, Tim Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Physical & theoretical chemistry ; Hydrogen Rydberg atoms ; surface ionisation ; resonant charge transfer