Rotational Spectroscopy of Simple Metal Carbon Clusters: Resolving the Beauty of Fine and Hyperfine Interactions in Metal Monoacetylides and Metal Carbides

Persistent Link:
http://hdl.handle.net/10150/603492
Title:
Rotational Spectroscopy of Simple Metal Carbon Clusters: Resolving the Beauty of Fine and Hyperfine Interactions in Metal Monoacetylides and Metal Carbides
Author:
Randtke, Jie Min
Issue Date:
2016
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:
Pure rotational spectra of simple metal carbon clusters that relevant to transition metal synthesis and catalysis have been obtained using Fourier transform microwave (FTMW) techniques combined with millimeter-wave direct-absorption methods. Rotational spectra of metal acetylides (CuCCH, ZnCCH, Li/Na/KCCH, MgCCH, AlCCH, CrCCH), diatomic metal monocarbide (CrC) and T-shape metal dicarbides (YC₂ and ScC₂) were recorded in the 4–650 GHz frequency regime. Measurements of weaker isotoplogues including ⁶⁶ZnCCH, ⁶⁸ZnCCH, Zn¹³C¹³CH, ZnCCD, Li/Na/KCCD, CrCCD, Y¹³C¹²C, Y¹³C¹³C, Sc¹³C¹³C, were also studied to aid in structural determinations. This work is the first study of ZnCCH and ScC₂ by any type of spectroscopic technique. Hyperfine splittings in MgCCH and Li/Na/KCCH have also been resolved and the weak isotoplogues of YC₂ have been measured for the first time. Potential interstellar molecules ScO and FeCN were studied using the FTMW techniques in the 4–62 GHz frequency regime. Spectra of the zinc insertion product ClZnCH₃ were additionally recorded in the 10–30 GHz (FTMW) and 260–296 GHz (direct absorption) frequency ranges, along with weaker isotopologues Cl⁶⁶ZnCH₃ and Cl⁶⁸ZnCH₃. This works is the first measurement of zinc insertion products using the FTMW-DALAS techniques. The data were analyzed implementing an effective Hamiltonian, allowing for accurate spectroscopic parameters to be established. From rotational constants, the molecular geometries were accurately determined. Electronic properties were also assessed, including the degree of covalent vs ionic character in a chemical bond, and the molecular orbital composition. The fundamental physical and chemical properties of these benchmark species were obtained in order to gain insight into their role in larger molecular systems, test theoretical calculations, and, in certain cases, provide accurate rest frequencies for astronomical searches.
Type:
text; Electronic Dissertation
Keywords:
Transition Metal; Chemistry; Rotational Spectroscopy
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Graduate College; Chemistry
Degree Grantor:
University of Arizona
Advisor:
Ziurys, Lucy M.

Full metadata record

DC FieldValue Language
dc.language.isoen_USen
dc.titleRotational Spectroscopy of Simple Metal Carbon Clusters: Resolving the Beauty of Fine and Hyperfine Interactions in Metal Monoacetylides and Metal Carbidesen_US
dc.creatorRandtke, Jie Minen
dc.contributor.authorRandtke, Jie Minen
dc.date.issued2016en
dc.publisherThe University of Arizona.en
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
dc.description.abstractPure rotational spectra of simple metal carbon clusters that relevant to transition metal synthesis and catalysis have been obtained using Fourier transform microwave (FTMW) techniques combined with millimeter-wave direct-absorption methods. Rotational spectra of metal acetylides (CuCCH, ZnCCH, Li/Na/KCCH, MgCCH, AlCCH, CrCCH), diatomic metal monocarbide (CrC) and T-shape metal dicarbides (YC₂ and ScC₂) were recorded in the 4–650 GHz frequency regime. Measurements of weaker isotoplogues including ⁶⁶ZnCCH, ⁶⁸ZnCCH, Zn¹³C¹³CH, ZnCCD, Li/Na/KCCD, CrCCD, Y¹³C¹²C, Y¹³C¹³C, Sc¹³C¹³C, were also studied to aid in structural determinations. This work is the first study of ZnCCH and ScC₂ by any type of spectroscopic technique. Hyperfine splittings in MgCCH and Li/Na/KCCH have also been resolved and the weak isotoplogues of YC₂ have been measured for the first time. Potential interstellar molecules ScO and FeCN were studied using the FTMW techniques in the 4–62 GHz frequency regime. Spectra of the zinc insertion product ClZnCH₃ were additionally recorded in the 10–30 GHz (FTMW) and 260–296 GHz (direct absorption) frequency ranges, along with weaker isotopologues Cl⁶⁶ZnCH₃ and Cl⁶⁸ZnCH₃. This works is the first measurement of zinc insertion products using the FTMW-DALAS techniques. The data were analyzed implementing an effective Hamiltonian, allowing for accurate spectroscopic parameters to be established. From rotational constants, the molecular geometries were accurately determined. Electronic properties were also assessed, including the degree of covalent vs ionic character in a chemical bond, and the molecular orbital composition. The fundamental physical and chemical properties of these benchmark species were obtained in order to gain insight into their role in larger molecular systems, test theoretical calculations, and, in certain cases, provide accurate rest frequencies for astronomical searches.en
dc.typetexten
dc.typeElectronic Dissertationen
dc.subjectTransition Metalen
dc.subjectChemistryen
dc.subjectRotational Spectroscopyen
thesis.degree.namePh.D.en
thesis.degree.leveldoctoralen
thesis.degree.disciplineGraduate Collegeen
thesis.degree.disciplineChemistryen
thesis.degree.grantorUniversity of Arizonaen
dc.contributor.advisorZiurys, Lucy M.en
dc.contributor.committeememberZiurys, Lucy M.en
dc.contributor.committeememberBrown, Michaelen
dc.contributor.committeememberMiranda, Katrinaen
dc.contributor.committeememberSanov, Andreien
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