The theory and EPR spectra of linear free radicals

Abstract

This dissertation is concerned mainly with the theory needed to explain the gas-phase electron paramagnetic resonance spectra of linear free radicals.
The Hamiltonian operator describing the system is obtained by transforming the Pauli-Schrodinger form of the Breit equation from a space-fixed to a molecule-fixed axis system. From this an effective Hamiltonian, operating in just the ground vibronic state is derived. This is then used to interpret the e.p.r, spectra of NS and CF. We obtain the electric dipole moment and information on the hyperfine parameters of these radicals.
The theory applicable to the energy levels of linear triatomic molecules is derived and the effects of the bending vibration on the e.p.r. spectra are obtained. Finally, the effects of case (c) coupling on the spectra of diatomic molecules are discussed; it is proposed that these are the cause of the discrepancies observed in the spectra of certain heavy molecules.

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