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Title: The LMR spectra of free radicals
Author: Towle, Jonathan Peter
ISNI:       0000 0001 3535 6902
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 1992
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Laser Magnetic Resonance (LMR) is a very sensitive, accurate and high resolution spectroscopic technique. Transitions of paramagnetic species are brought into coincidence with a fixed frequency laser using Zeeman tuning. Three different LMR spectrometers are described, two of which use the CO laser as a radiation source and the other used optically pumped far-infrared lasers. These LMR spectrometers have been used to study four radicals, germanium hydride (GeH), tellurium deuteride (TeD), iron hydride (FeH) and iron deuteride (FeD). Transitions in the fundamental and first hot bands of the GeH radical have been detected by CO LMR. The transitions occur within both 2Π1andfrasl;2 and 2Π3andfrasl;2 manifolds. These data have been fitted with previously published data for GeH and GeD to determine the parameters of a single model effective Hamiltonian which describes all naturally occurring isotopomers. Details of the Hamiltonian are given. The same Hamiltonian was used to model transitions in the fundamental and first two hot bands of the TeD radical that were also recorded using CO LMR. Resonances from the seven most abundant isotopomers, including the two with I = ½, have been identified. Seven transitions in the fundamental band of FeH have been observed using Faraday CO LMR. Due to the complicated electronic structure for FeH it is not possible to model these data using a single model effective Hamiltonian. It has been possible to fit the parameters of a second order Zeeman expression to these FeH data and so determine accurate zerofield transition wavenumbers for six of these transitions. Pure rotational transitions in the ground state of FeD have been observed using FIR LMR. As for FeH the parameters of second order Zeeman expressions can be fitted to these transitions and zero field wavenumbers determined.
Supervisor: Brown, John M. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Free radicals (Chemistry) ; Magnetic resonance ; Infrared spectra