THEORETICAL AND EXPERIMENTAL ASPECTS OF THE ROTATIONAL SPECTROSCOPY OF SMALL MOLECULES

Persistent Link:
http://hdl.handle.net/10150/282041
Title:
THEORETICAL AND EXPERIMENTAL ASPECTS OF THE ROTATIONAL SPECTROSCOPY OF SMALL MOLECULES
Author:
Fry, Herbert Alan
Issue Date:
1981
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)
Keywords:
Cyanogen compounds -- Spectra.; Deuterium compounds -- Spectra.
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Graduate College; Chemistry
Degree Grantor:
University of Arizona
Advisor:
Kukolich, Stephen G.

Full metadata record

DC FieldValue Language
dc.language.isoen_USen_US
dc.titleTHEORETICAL AND EXPERIMENTAL ASPECTS OF THE ROTATIONAL SPECTROSCOPY OF SMALL MOLECULESen_US
dc.creatorFry, Herbert Alanen_US
dc.contributor.authorFry, Herbert Alanen_US
dc.date.issued1981en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © 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.en_US
dc.description.abstractTheoretical 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.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectCyanogen compounds -- Spectra.en_US
dc.subjectDeuterium compounds -- Spectra.en_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorKukolich, Stephen G.en_US
dc.identifier.proquest8202549en_US
dc.identifier.oclc8705361en_US
dc.identifier.bibrecord.b13912379en_US
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