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Some theoretical and experimental aspects of gas phase E.P.R. spectroscopy

Some theoretical and experimental aspects of gas phase E.P.R. spectroscopy
Some theoretical and experimental aspects of gas phase E.P.R. spectroscopy

The derivation of an effective rotational Hamiltonian is discussed. Using these general techniques some spin-dependent interactions in Estates of quartet and higher multiplicity are cast into operator equivalent form. As a result the two spin-rotation constants required, in principle, for 4F states are shown to be the same to within experimental error. These results are generalised to cover states of higher multiplicity. A fourth order spin-spin interaction arising in 5E: states is investigated.The rotational energy levels of a molecule in a 2TT electronic state are described, with particular reference to the OH radical, and some higher order A-doubling and hyperfine interactions are cast into operator equivalent form. A comparison is made with effective rotational Hamiltonians used by other workers. A reanalysis of the zero-field A-doubling frequencies for OH is outlined. Other higher order interactions appear to be needed to further improve the fit.The measurement of the gas phase e.p.r. spectrum arising from the 2TT3/2J = 9/2 rotational levels of OH is detailed and the theory of the g-factors in 27T states is given. Values for molecular g-factors determined from an analysis of e.p.r. measurements on seven rotational levels of OH are quoted, and compared with a pure precession model. Effective g-factors are calculated from these molecular g -factors and compared with published experimental results.Some initial experiments investigating the possibility of using pyrolysis to generate radicals for gas phase e.p.r. studies are detailed.

University of Southampton
Milton, David John
Milton, David John

Milton, David John (1976) Some theoretical and experimental aspects of gas phase E.P.R. spectroscopy. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

The derivation of an effective rotational Hamiltonian is discussed. Using these general techniques some spin-dependent interactions in Estates of quartet and higher multiplicity are cast into operator equivalent form. As a result the two spin-rotation constants required, in principle, for 4F states are shown to be the same to within experimental error. These results are generalised to cover states of higher multiplicity. A fourth order spin-spin interaction arising in 5E: states is investigated.The rotational energy levels of a molecule in a 2TT electronic state are described, with particular reference to the OH radical, and some higher order A-doubling and hyperfine interactions are cast into operator equivalent form. A comparison is made with effective rotational Hamiltonians used by other workers. A reanalysis of the zero-field A-doubling frequencies for OH is outlined. Other higher order interactions appear to be needed to further improve the fit.The measurement of the gas phase e.p.r. spectrum arising from the 2TT3/2J = 9/2 rotational levels of OH is detailed and the theory of the g-factors in 27T states is given. Values for molecular g-factors determined from an analysis of e.p.r. measurements on seven rotational levels of OH are quoted, and compared with a pure precession model. Effective g-factors are calculated from these molecular g -factors and compared with published experimental results.Some initial experiments investigating the possibility of using pyrolysis to generate radicals for gas phase e.p.r. studies are detailed.

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Published date: 1976

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Local EPrints ID: 462533
URI: http://eprints.soton.ac.uk/id/eprint/462533
PURE UUID: e8b42df2-ff78-4291-b909-abf0d68cd5e5

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Date deposited: 04 Jul 2022 19:16
Last modified: 04 Jul 2022 21:23

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Author: David John Milton

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