{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/112994"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/112994","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Development of solution-phase extreme ultraviolet spectroscopy and photophysics of μ-oxo-bridged Fe(III)porphyrins","abstract":"A sample delivery method is developed to extend the field of transient M-edge x-ray absorption spectroscopy to study molecular complexes in the solution-phase. A gas-accelerated liquid sheet method is adapted to operate in the vacuum conditions needed for XUV transmission. Gas-generated liquid sheet of chlorinated solvents transmissible to XUV photons are characterized and stabilized under vacuum conditions. A method for measuring the thickness of a liquid sheet in situ is described and the high-pressure pumping system for generating the liquid sheet is detailed. The instrument for M-edge absorption spectroscopy is adapted to handle the gas load for the vacuum chambers. The first transmission spectrum of XUV in the energy of 40-90 eV is collected through a flowing liquid sheet of dichloroethane. It is determined that with the noise level present in the liquid sheet, a transient spectrum of a liquid sheet containing FeTPPCl could be collected with a reasonable signal to noise ratio. However, it is found that the liquid sheet of an iron monoporphyrin was unstable in the XUV sample chamber under high vacuum conditions. The transient M-edge absorption spectroscopy technique is also used to probe the excited state dynamics of an iron stacked porphyrin, (TPPFe)2O, oxidation catalyst in the solid state. The relaxation pathway upon photoexcitation at several pump wavelengths is studied to determine the stability and lifetime of the catalytically active Fe(IV)oxo intermediate state. With a combination of optical and XUV absorption techniques, it is found that upon excitation, the stacked porphyrin formed an Fe(II)/Fe(III) containing LMCT state which decays in less than 1 ps. The remaining excited states of the stacked porphyrin are XUV dark and are identified as a relaxing through the pathway containing an Fe(III)TPP+ and Fe(III)TPPO- subunits with the charges on the porphyrin ligand. It is found that the Fe(IV)oxo intermediate state is not observed in these studies and is likely a small percentage of the relaxation pathway.","abstract_html":"A sample delivery method is developed to extend the field of transient M-edge x-ray absorption spectroscopy to study molecular complexes in the solution-phase. A gas-accelerated liquid sheet method is adapted to operate in the vacuum conditions needed for XUV transmission. Gas-generated liquid sheet of chlorinated solvents transmissible to XUV photons are characterized and stabilized under vacuum conditions. A method for measuring the thickness of a liquid sheet in situ is described and the high-pressure pumping system for generating the liquid sheet is detailed. The instrument for M-edge absorption spectroscopy is adapted to handle the gas load for the vacuum chambers. The first transmission spectrum of XUV in the energy of 40-90 eV is collected through a flowing liquid sheet of dichloroethane. It is determined that with the noise level present in the liquid sheet, a transient spectrum of a liquid sheet containing FeTPPCl could be collected with a reasonable signal to noise ratio. However, it is found that the liquid sheet of an iron monoporphyrin was unstable in the XUV sample chamber under high vacuum conditions. The transient M-edge absorption spectroscopy technique is also used to probe the excited state dynamics of an iron stacked porphyrin, (TPPFe)2O, oxidation catalyst in the solid state. The relaxation pathway upon photoexcitation at several pump wavelengths is studied to determine the stability and lifetime of the catalytically active Fe(IV)oxo intermediate state. With a combination of optical and XUV absorption techniques, it is found that upon excitation, the stacked porphyrin formed an Fe(II)/Fe(III) containing LMCT state which decays in less than 1 ps. The remaining excited states of the stacked porphyrin are XUV dark and are identified as a relaxing through the pathway containing an Fe(III)TPP+ and Fe(III)TPPO- subunits with the charges on the porphyrin ligand. It is found that the Fe(IV)oxo intermediate state is not observed in these studies and is likely a small percentage of the relaxation pathway.","abstract_has_math":false,"creators":["Sye, Kori Marie"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Vura-Weis, Josh","Fout, Alison R","Han, Hee-Sun","Backlund, Mikael"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022-01-12T21:45:28Z","date_published":"2022-01-12T21:45:28Z","updated_at":"2026-07-22T22:24:52Z","subjects":["extreme ultraviolet spectroscopy","transient M-edge spectroscopy","solution-phase XUV absorption","stacked iron porphyrin","Fe(IV)oxo","excited state dynamics"],"languages":["en"],"rights":["Copyright 2021 Kori Sye"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/112994","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Vura-Weis, Josh","Fout, Alison R","Han, Hee-Sun","Backlund, Mikael"]},{"key":"dc:creator","label":"Author","values":["Sye, Kori Marie"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2022-01-12T21:45:28Z","2021-07-09","2021-08"]},{"key":"dc:type","label":"Dc Type","values":["text","Thesis"]},{"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":["extreme ultraviolet spectroscopy","transient M-edge spectroscopy","solution-phase XUV absorption","stacked iron porphyrin","Fe(IV)oxo","excited state dynamics"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2021 Kori Sye"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/112994"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["A sample delivery method is developed to extend the field of transient M-edge x-ray absorption spectroscopy to study molecular complexes in the solution-phase. A gas-accelerated liquid sheet method is adapted to operate in the vacuum conditions needed for XUV transmission. Gas-generated liquid sheet of chlorinated solvents transmissible to XUV photons are characterized and stabilized under vacuum conditions. A method for measuring the thickness of a liquid sheet in situ is described and the high-pressure pumping system for generating the liquid sheet is detailed. The instrument for M-edge absorption spectroscopy is adapted to handle the gas load for the vacuum chambers. The first transmission spectrum of XUV in the energy of 40-90 eV is collected through a flowing liquid sheet of dichloroethane. It is determined that with the noise level present in the liquid sheet, a transient spectrum of a liquid sheet containing FeTPPCl could be collected with a reasonable signal to noise ratio. However, it is found that the liquid sheet of an iron monoporphyrin was unstable in the XUV sample chamber under high vacuum conditions. The transient M-edge absorption spectroscopy technique is also used to probe the excited state dynamics of an iron stacked porphyrin, (TPPFe)2O, oxidation catalyst in the solid state. The relaxation pathway upon photoexcitation at several pump wavelengths is studied to determine the stability and lifetime of the catalytically active Fe(IV)oxo intermediate state. With a combination of optical and XUV absorption techniques, it is found that upon excitation, the stacked porphyrin formed an Fe(II)/Fe(III) containing LMCT state which decays in less than 1 ps. The remaining excited states of the stacked porphyrin are XUV dark and are identified as a relaxing through the pathway containing an Fe(III)TPP+ and Fe(III)TPPO- subunits with the charges on the porphyrin ligand. It is found that the Fe(IV)oxo intermediate state is not observed in these studies and is likely a small percentage of the relaxation pathway.","Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2022-01-12 without embargo terms","The student, Kori Sye, accepted the attached license on 2021-07-07 at 16:06.","The student, Kori Sye, submitted this Dissertation for approval on 2021-07-07 at 16:16.","This Dissertation was approved for publication on 2021-07-09 at 17:03.","DSpace SAF Submission Ingestion Package generated from Vireo submission #16786 on 2022-01-12 at 12:44:17","Made available in DSpace on 2022-01-12T21:45:28Z (GMT). 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A gas-accelerated liquid sheet method is adapted to operate in the vacuum conditions needed for XUV transmission. Gas-generated liquid sheet of chlorinated solvents transmissible to XUV photons are characterized and stabilized under vacuum conditions. A method for measuring the thickness of a liquid sheet in situ is described and the high-pressure pumping system for generating the liquid sheet is detailed. The instrument for M-edge absorption spectroscopy is adapted to handle the gas load for the vacuum chambers. The first transmission spectrum of XUV in the energy of 40-90 eV is collected through a flowing liquid sheet of dichloroethane. It is determined that with the noise level present in the liquid sheet, a transient spectrum of a liquid sheet containing FeTPPCl could be collected with a reasonable signal to noise ratio. However, it is found that the liquid sheet of an iron monoporphyrin was unstable in the XUV sample chamber under high vacuum conditions. The transient M-edge absorption spectroscopy technique is also used to probe the excited state dynamics of an iron stacked porphyrin, (TPPFe)2O, oxidation catalyst in the solid state. The relaxation pathway upon photoexcitation at several pump wavelengths is studied to determine the stability and lifetime of the catalytically active Fe(IV)oxo intermediate state. With a combination of optical and XUV absorption techniques, it is found that upon excitation, the stacked porphyrin formed an Fe(II)/Fe(III) containing LMCT state which decays in less than 1 ps. The remaining excited states of the stacked porphyrin are XUV dark and are identified as a relaxing through the pathway containing an Fe(III)TPP+ and Fe(III)TPPO- subunits with the charges on the porphyrin ligand. It is found that the Fe(IV)oxo intermediate state is not observed in these studies and is likely a small percentage of the relaxation pathway.","Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2022-01-12 without embargo terms","The student, Kori Sye, accepted the attached license on 2021-07-07 at 16:06.","The student, Kori Sye, submitted this Dissertation for approval on 2021-07-07 at 16:16.","This Dissertation was approved for publication on 2021-07-09 at 17:03.","DSpace SAF Submission Ingestion Package generated from Vireo submission #16786 on 2022-01-12 at 12:44:17","Made available in DSpace on 2022-01-12T21:45:28Z (GMT). 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