{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/20114"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/20114","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Characterization of metal sites. I. In molybdoenzymes and their model systems, and, II. On silver electrode surfaces","abstract":"In part 1 of this thesis, the characterization of molybdenum complexes and some molybdoenzymes was made through the use of optical and magnetic circular dichroism (MCD) spectroscopy. MCD spectra were obtained for (MOCl$\\sb4$) $\\sp-$ (M = Cr, and Mo) and (WOCl$\\sb4$(H$\\sb2$O)) $\\sp-$ compounds. All of the spectra display temperature and field dependence consistent with a paramagnetic ground state. The two lowest energy bands are assigned to the $d\\sb{xy} \\to d\\sb{xz},d\\sb{yz}$ and $d\\sb{xy} \\to d\\sb{x\\sp2-y\\sp2}$ ligand field transitions. All of the compounds display vibronic structure on the $d\\sb{xy} \\to d\\sb{xz},d\\sb{yz}$ band arising from coupling with the totally symmetric M-O stretch. The third band is assigned to a b$\\sb1$(Cl) to b$\\sb2(d\\sb{xy})$ charge transfer transition and at slightly higher energies are charge transfer transitions from orbitals with e symmetry to the half occupied $d\\sb{xy}$ orbital.","abstract_html":"In part 1 of this thesis, the characterization of molybdenum complexes and some molybdoenzymes was made through the use of optical and magnetic circular dichroism (MCD) spectroscopy. MCD spectra were obtained for (MOCl$\\sb4$) $\\sp-$ (M = Cr, and Mo) and (WOCl$\\sb4$(H$\\sb2$O)) $\\sp-$ compounds. All of the spectra display temperature and field dependence consistent with a paramagnetic ground state. The two lowest energy bands are assigned to the $d\\sb{xy} \\to d\\sb{xz},d\\sb{yz}$ and $d\\sb{xy} \\to d\\sb{x\\sp2-y\\sp2}$ ligand field transitions. All of the compounds display vibronic structure on the $d\\sb{xy} \\to d\\sb{xz},d\\sb{yz}$ band arising from coupling with the totally symmetric M-O stretch. The third band is assigned to a b$\\sb1$(Cl) to b$\\sb2(d\\sb{xy})$ charge transfer transition and at slightly higher energies are charge transfer transitions from orbitals with e symmetry to the half occupied $d\\sb{xy}$ orbital.","abstract_has_math":true,"creators":["Sabel, Dawn M."],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Gewirth, Andrew A."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T12:29:15Z","date_published":"2011-05-07T12:29:15Z","updated_at":"2026-07-22T22:25:15Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1993 Sabel, Dawn M."],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9411772","(UMI)AAI9411772"],"render_values":[{"text":"AAI9411772","href":null,"code":true},{"text":"(UMI)AAI9411772","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/20114","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Gewirth, Andrew A."]},{"key":"dc:creator","label":"Author","values":["Sabel, Dawn M."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T12:29:15Z","10000-01-01","1993"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Inorganic"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1993 Sabel, Dawn M."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9411772","(UMI)AAI9411772","http://hdl.handle.net/2142/20114"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["In part 1 of this thesis, the characterization of molybdenum complexes and some molybdoenzymes was made through the use of optical and magnetic circular dichroism (MCD) spectroscopy. MCD spectra were obtained for (MOCl$\\sb4$) $\\sp-$ (M = Cr, and Mo) and (WOCl$\\sb4$(H$\\sb2$O)) $\\sp-$ compounds. All of the spectra display temperature and field dependence consistent with a paramagnetic ground state. The two lowest energy bands are assigned to the $d\\sb{xy} \\to d\\sb{xz},d\\sb{yz}$ and $d\\sb{xy} \\to d\\sb{x\\sp2-y\\sp2}$ ligand field transitions. All of the compounds display vibronic structure on the $d\\sb{xy} \\to d\\sb{xz},d\\sb{yz}$ band arising from coupling with the totally symmetric M-O stretch. The third band is assigned to a b$\\sb1$(Cl) to b$\\sb2(d\\sb{xy})$ charge transfer transition and at slightly higher energies are charge transfer transitions from orbitals with e symmetry to the half occupied $d\\sb{xy}$ orbital.","MCD spectra were also obtained for (MoOBr$\\sb4$(H$\\sb2$O)) $\\sp-,$ (MoO(SPh)$\\sb4\\rbrack\\sp-$ and Rhodobacter sphaeroides dimethyl sulfoxide (DMSO) reductase. The latter two display charge transfer transitions at significantly lower energies than observed in the (MOCl$\\sb4\\rbrack\\sp-$ complexes which is consistent with thiol coordination. The rich charge transfer region of the DMSO reductase spectrum appears consist with dithiolene linkage.","Part 2 of this thesis, metal surfaces have been characterized through the use of atomic force microscopy (AFM). The AFM was used to examine the interaction of anions with the Ag(111) electrode. It was found that perchlorate and chloride anions are not inert to the Ag(111) surface while sulfate ions do not perturb the system noticeably. In situ AFM images of underpotential deposition of Cd adlayers on Ag(111) were also collected. After the first deposition peak, the Cd forms a $(\\surd3$ x $\\surd3)$R30$\\sp\\circ$ adlattice. Deposition of a full monolayer of Cd followed by short polarization times induces the formation of a Cd/Ag alloy. Dissolution of Cd from this alloy is characterized by surface roughening and the formation of pits which diffuse across the surface.","Made available in DSpace on 2011-05-07T12:29:15Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9411772.pdf: 6498827 bytes, checksum: 45a848d9edc8a4ece4a50967d7d63b52 (MD5) Previous issue date: 1993","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:41:39Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:18:03-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["Characterization of metal sites. I. In molybdoenzymes and their model systems, and, II. On silver electrode surfaces"]}]}],"canonical_facts":{"dc:contributor":["Gewirth, Andrew A."],"dc:creator":["Sabel, Dawn M."],"dc:date":["2011-05-07T12:29:15Z","10000-01-01","1993"],"dc:description":["In part 1 of this thesis, the characterization of molybdenum complexes and some molybdoenzymes was made through the use of optical and magnetic circular dichroism (MCD) spectroscopy. MCD spectra were obtained for (MOCl$\\sb4$) $\\sp-$ (M = Cr, and Mo) and (WOCl$\\sb4$(H$\\sb2$O)) $\\sp-$ compounds. All of the spectra display temperature and field dependence consistent with a paramagnetic ground state. The two lowest energy bands are assigned to the $d\\sb{xy} \\to d\\sb{xz},d\\sb{yz}$ and $d\\sb{xy} \\to d\\sb{x\\sp2-y\\sp2}$ ligand field transitions. All of the compounds display vibronic structure on the $d\\sb{xy} \\to d\\sb{xz},d\\sb{yz}$ band arising from coupling with the totally symmetric M-O stretch. The third band is assigned to a b$\\sb1$(Cl) to b$\\sb2(d\\sb{xy})$ charge transfer transition and at slightly higher energies are charge transfer transitions from orbitals with e symmetry to the half occupied $d\\sb{xy}$ orbital.","MCD spectra were also obtained for (MoOBr$\\sb4$(H$\\sb2$O)) $\\sp-,$ (MoO(SPh)$\\sb4\\rbrack\\sp-$ and Rhodobacter sphaeroides dimethyl sulfoxide (DMSO) reductase. The latter two display charge transfer transitions at significantly lower energies than observed in the (MOCl$\\sb4\\rbrack\\sp-$ complexes which is consistent with thiol coordination. The rich charge transfer region of the DMSO reductase spectrum appears consist with dithiolene linkage.","Part 2 of this thesis, metal surfaces have been characterized through the use of atomic force microscopy (AFM). The AFM was used to examine the interaction of anions with the Ag(111) electrode. It was found that perchlorate and chloride anions are not inert to the Ag(111) surface while sulfate ions do not perturb the system noticeably. In situ AFM images of underpotential deposition of Cd adlayers on Ag(111) were also collected. After the first deposition peak, the Cd forms a $(\\surd3$ x $\\surd3)$R30$\\sp\\circ$ adlattice. Deposition of a full monolayer of Cd followed by short polarization times induces the formation of a Cd/Ag alloy. Dissolution of Cd from this alloy is characterized by surface roughening and the formation of pits which diffuse across the surface.","Made available in DSpace on 2011-05-07T12:29:15Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9411772.pdf: 6498827 bytes, checksum: 45a848d9edc8a4ece4a50967d7d63b52 (MD5) Previous issue date: 1993","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:41:39Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:18:03-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["AAI9411772","(UMI)AAI9411772","http://hdl.handle.net/2142/20114"],"dc:language":["eng"],"dc:rights":["Copyright 1993 Sabel, Dawn M."],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Characterization of metal sites. I. In molybdoenzymes and their model systems, and, II. On silver electrode surfaces"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:15Z"}