High Resolution Millimeter-Wave Spectroscopy of Metal Hydrosulfides and Imides

Persistent Link:
http://hdl.handle.net/10150/193521
Title:
High Resolution Millimeter-Wave Spectroscopy of Metal Hydrosulfides and Imides
Author:
Janczyk, Alexandra Julia
Issue Date:
2005
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:
The aim of rotational spectroscopy is to investigate the structure and the bonding character in molecules. Using millimeter-submillimeter experimental techniques, molecules are typically investigated in the ground electronic state. Therefore, one of the advantages of employing rotational spectroscopy is to determine the ground electronic state of the species under investigation. There are three different classes of molecules that are presented in this thesis: diatomic species (BaS), linear triatomic species (BaNH) and asymmetric tops LiSH, BaSH, CuSH and AlSH, including their isotopomers. Although the initial data for the BaS has been published, new rotational transitions are included in the initial data set to optimize the rotational constants for this species and its six isotopomers. The BaNH molecule is the first alkaline earth imide investigated in the gas phase. The spectroscopic data of the main isotope and its lesser isotopomers indicate a linear structure. DFT calculations suggest that the linear structure is a result of the pi bond between barium and nitrogen. The metal hydrosulfides studied here are asymmetric tops. LiSH, BaSH, CuSH and AlSH were found to be bent with an angle oscillating around 90 deg.. Since the bond angle of 90 deg. is close to that of H2S, it is believed that the sulfur p orbitals bond to metal and hydrogen. The hydroxide counterparts of the hydrosulfides that have been studied experimentally are either linear or quasilinear. The one exception thus far is CuOH, which is bent with an angle of 110 deg.. The hydrosulfide species are believed to have covalent bonding, in contrast to the metal hydroxides, which primarily have ionic bond character. The only investigated radical is the asymmetric top molecule, BaSH. The additional spin rotational terms along three molecular axes epsilon(aa), epsilon(bb), epsilon(cc) give insight into the non-spherical distribution of the one unpaired electron of the metal atom in its ground state. The non-spherical distribution has been explained by the presence of p(pi) character, which was mixed into the ground state from the nearby excited electronic states: A' and A''.
Type:
text; Electronic Dissertation
Degree Name:
PhD
Degree Level:
doctoral
Degree Program:
Chemistry; Graduate College
Degree Grantor:
University of Arizona
Advisor:
Ziurys, Lucy M.
Committee Chair:
Ziurys, Lucy M.

Full metadata record

DC FieldValue Language
dc.language.isoENen_US
dc.titleHigh Resolution Millimeter-Wave Spectroscopy of Metal Hydrosulfides and Imidesen_US
dc.creatorJanczyk, Alexandra Juliaen_US
dc.contributor.authorJanczyk, Alexandra Juliaen_US
dc.date.issued2005en_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.abstractThe aim of rotational spectroscopy is to investigate the structure and the bonding character in molecules. Using millimeter-submillimeter experimental techniques, molecules are typically investigated in the ground electronic state. Therefore, one of the advantages of employing rotational spectroscopy is to determine the ground electronic state of the species under investigation. There are three different classes of molecules that are presented in this thesis: diatomic species (BaS), linear triatomic species (BaNH) and asymmetric tops LiSH, BaSH, CuSH and AlSH, including their isotopomers. Although the initial data for the BaS has been published, new rotational transitions are included in the initial data set to optimize the rotational constants for this species and its six isotopomers. The BaNH molecule is the first alkaline earth imide investigated in the gas phase. The spectroscopic data of the main isotope and its lesser isotopomers indicate a linear structure. DFT calculations suggest that the linear structure is a result of the pi bond between barium and nitrogen. The metal hydrosulfides studied here are asymmetric tops. LiSH, BaSH, CuSH and AlSH were found to be bent with an angle oscillating around 90 deg.. Since the bond angle of 90 deg. is close to that of H2S, it is believed that the sulfur p orbitals bond to metal and hydrogen. The hydroxide counterparts of the hydrosulfides that have been studied experimentally are either linear or quasilinear. The one exception thus far is CuOH, which is bent with an angle of 110 deg.. The hydrosulfide species are believed to have covalent bonding, in contrast to the metal hydroxides, which primarily have ionic bond character. The only investigated radical is the asymmetric top molecule, BaSH. The additional spin rotational terms along three molecular axes epsilon(aa), epsilon(bb), epsilon(cc) give insight into the non-spherical distribution of the one unpaired electron of the metal atom in its ground state. The non-spherical distribution has been explained by the presence of p(pi) character, which was mixed into the ground state from the nearby excited electronic states: A' and A''.en_US
dc.typetexten_US
dc.typeElectronic Dissertationen_US
thesis.degree.namePhDen_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorZiurys, Lucy M.en_US
dc.contributor.chairZiurys, Lucy M.en_US
dc.contributor.committeememberSanov, Andreien_US
dc.contributor.committeememberLichtenberger, Dennisen_US
dc.contributor.committeememberEnemark, Johnen_US
dc.contributor.committeememberBrown, Michaelen_US
dc.identifier.proquest1349en_US
dc.identifier.oclc137355167en_US
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