Part I. Rates of Paramagnetic Pulse Reactions by Nuclear Magnetic Resonance. Part II. The Electron Paramagnetic Resonance Spectrum of Gas Phase ¹⁴N¹⁶0₂ and its Pressure Dependence

Citation

Berger, Stuart Brooke (1961) Part I. Rates of Paramagnetic Pulse Reactions by Nuclear Magnetic Resonance. Part II. The Electron Paramagnetic Resonance Spectrum of Gas Phase ¹⁴N¹⁶0₂ and its Pressure Dependence. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/NTDW-4N34. https://resolver.caltech.edu/CaltechETD:etd-03302006-112606

Abstract

NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document. Part I of this thesis concerns the classically derived theory of the effect on the nuclear magnetic resonance line width and shape of a species which has a nucleus under investigation and is involved in an electron exchange reaction. The result is that the pseudo-first order reaction rate constant is added, under certain conditions, directly onto the no electron exchange line width of the species investigated, thereby increasing that line width. A reprint of a published article is included. Part II of this thesis concerns the investigation of the gas phase E.P.R. spectrum of nitrogen 14, oxygen-16 at a total pressure of 0.65 millimeters of mercury to 1.3 atmospheres. A many lined spectrum is recorded at low pressures which upon increase of pressure loses intensity in the portion away from the center of the spectrum and gains intensity in the central region, especially in three positions. Upon further increase in pressure the many lines broaden into a triplet at the three positions cited which continues to broaden with increase of pressure, eventually forming a singlet. This singlet continues to broaden with increase in pressure. A linear relation between line width and pressure is approached at the intermediate to high end of the pressure range investigated. The data is consistent with the assignment of a Fermi contact interaction equal to 131 Mcps and a spin-rotation interaction equal to 73 Mcps. The comparison to the theory of the electronic distribution of NO2 and to the work done on the NO2 E.P.R. spectrum in liquid CS2 and CCl4 in the argon matrix is discussed. The broadening is interpreted in terms of the spin-rotation and spin-spin coupling (spin-lattice interaction) and collision theory. A treatment of the overlapping of three spectral lines at [...] and [...] is given.

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