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    THEORETICAL AND EXPERIMENTAL ASPECTS OF THE ROTATIONAL SPECTROSCOPY OF SMALL MOLECULES

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    Author
    Fry, Herbert Alan
    Issue Date
    1981
    Keywords
    Cyanogen compounds -- Spectra.
    Deuterium compounds -- Spectra.
    Advisor
    Kukolich, Stephen G.
    
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    Publisher
    The University of Arizona.
    Rights
    Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
    Abstract
    Theoretical and experimental aspects of high resolution spectroscopy are discussed. The theoretical work concentrates on the matrix elements of the rigid rotor and molecular hyperfine terms of the Hamiltonian of a rotating molecule. The experimental work consists of Stark cell and beam maser microwave spectroscopy on C1CN and HDO respectively. The theory of rotational spectroscopy is developed in a uniform manner based on the irreducible tensor method. It is shown how the effect of molecular symmetry may be incorporated into this method. The instrumentation required to observe the hyperfine splittings is discussed. This includes descriptions of the Stark cell and molecular beam maser microwave spectrometers. A new tunable C-band resonant cavity is described. The following molecular constants are reported for both common species of C1CN: rotational constant Bₒ, centrifugal distortion constant D(J), quadrupole coupling constant eqQ(k), and spin-rotation constant C(x). Values in MHz for C1CN are as follows: ³⁵C1CN; Bₒ = 5 907.820 ± 0.010, eqQ(C1) = -83.26 ± 0.06, eqQ(N) = -3.59 ± 0.08, C(C1) = -0.006 ± 0.006, C(N) = 0.013 ± 0.010; ³⁷C1CN; Bₒ = 5 847.246 ± 0.008, eqQ(C1) = -65.61 ± 0.06, eqQ(N) = -3.61 ± 0.08, C(C1) = -0.004 ± 0.006, C(N) = 0.010 ± 0.010. The following molecular constants for HDO are reported: quadrupole coupling tensor elements eqQ(D)(gg) and spin-rotation tensor elements C(x)(gg). The values in KHz are as follows: eqQ(D)(aa) = 276.45 ± .88, eqQ(D)(bb) = -110.97 ± 1.46, eqQ(D)(cc) = -165.77 ± 1.10, C(D)(aa) = 1.33 ± .20, C(D)(bb) = -4.38 ± .36, C(D)(cc) = -2.99 ± .24, C(H)(aa) = -58.42 ± .47, C(H)(bb) = -5.46 ± .83, C(H)(cc) = -23.28 ± .10. The values for the constants for C1CN agree with previous values but are more precise. Those for HDO do not agree with previous values but are thought to be more accurate since they are obtained for a larger data base.
    Type
    text
    Dissertation-Reproduction (electronic)
    Degree Name
    Ph.D.
    Degree Level
    doctoral
    Degree Program
    Graduate College
    Chemistry
    Degree Grantor
    University of Arizona
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