{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/78588"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/78588","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"High pressure surface enhanced Raman scattering spectroscopy","abstract":"Surface-enhanced Raman scattering spectroscopy (SERS) was combined with the diamond anvil cell technique to study molecular monolayers and single molecules under high pressure. Vibrational spectra up to 8 GPa were obtained for self-assembled monolayers (SAMs) of the energetic material simulant 4-nitrobenzenethiol (NBT). A large pressure-broadening NO2 symmetrical stretch was found in the SAMs but not in solid NBT. Single-molecule Raman spectra were studied at high pressures (1-4 GPa). The molecules were two isotopologues of the dye rhodamine 6G (R6G and d4-R6G), adsorbed on colloidal Ag particles immobilized in polyvinyl alcohol (PVA). The distributions of pressure-induced blueshifts and linewidths of individual molecules were obtained at different pressures. The linewidth of the single-molecule Raman spectra increased little with pressure, but the variations in blueshifts increased significantly and accounted for most of the pressure-broadening found in the ensemble Raman spectra. To study the pressure effect on plasmon-based electromagnetic enhancement, localized surface plasmon resonance (LSPR) spectra of a photonic substrate and Raman scattering spectra of bezenethiol (BT) monolayers adsorbed upon were measured simultaneously under high pressure. The LSPR split into two peaks under initial compression, and both peaks redshifted with further-increased pressure. The shifts in LSPR was correlated to the Raman intensity variations found in BT Raman spectra. These results suggest that both deformation in the nanoparticles and changes in the dielectric functions with pressure should be taken into account when designing SERS substrates intended for working at high pressures.","abstract_html":"Surface-enhanced Raman scattering spectroscopy (SERS) was combined with the diamond anvil cell technique to study molecular monolayers and single molecules under high pressure. Vibrational spectra up to 8 GPa were obtained for self-assembled monolayers (SAMs) of the energetic material simulant 4-nitrobenzenethiol (NBT). A large pressure-broadening NO2 symmetrical stretch was found in the SAMs but not in solid NBT. Single-molecule Raman spectra were studied at high pressures (1-4 GPa). The molecules were two isotopologues of the dye rhodamine 6G (R6G and d4-R6G), adsorbed on colloidal Ag particles immobilized in polyvinyl alcohol (PVA). The distributions of pressure-induced blueshifts and linewidths of individual molecules were obtained at different pressures. The linewidth of the single-molecule Raman spectra increased little with pressure, but the variations in blueshifts increased significantly and accounted for most of the pressure-broadening found in the ensemble Raman spectra. To study the pressure effect on plasmon-based electromagnetic enhancement, localized surface plasmon resonance (LSPR) spectra of a photonic substrate and Raman scattering spectra of bezenethiol (BT) monolayers adsorbed upon were measured simultaneously under high pressure. The LSPR split into two peaks under initial compression, and both peaks redshifted with further-increased pressure. The shifts in LSPR was correlated to the Raman intensity variations found in BT Raman spectra. These results suggest that both deformation in the nanoparticles and changes in the dielectric functions with pressure should be taken into account when designing SERS substrates intended for working at high pressures.","abstract_has_math":false,"creators":["Fu, Yuanxi"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Dlott, Dana","Gruebele, Martin","Bass, Jay D.","Granick, Steve"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-07-22T22:32:54Z","date_published":"2015-07-22T22:32:54Z","updated_at":"2026-07-22T22:26:12Z","subjects":["single-molecule spectroscopy","diamond anvil cell","surface enhanced Raman scattering spectroscopy","High pressure"],"languages":[],"rights":["Copyright 2015 Yuanxi Fu"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/78588","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Dlott, Dana","Gruebele, Martin","Bass, Jay D.","Granick, Steve"]},{"key":"dc:creator","label":"Author","values":["Fu, Yuanxi"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-07-22T22:32:54Z","2017-07-23T09:15:24Z","2015-05","2015-03-05","2015-5"]},{"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":["single-molecule spectroscopy","diamond anvil cell","surface enhanced Raman scattering spectroscopy","High pressure"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2015 Yuanxi Fu"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/78588"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Surface-enhanced Raman scattering spectroscopy (SERS) was combined with the diamond anvil cell technique to study molecular monolayers and single molecules under high pressure. Vibrational spectra up to 8 GPa were obtained for self-assembled monolayers (SAMs) of the energetic material simulant 4-nitrobenzenethiol (NBT). A large pressure-broadening NO2 symmetrical stretch was found in the SAMs but not in solid NBT. Single-molecule Raman spectra were studied at high pressures (1-4 GPa). The molecules were two isotopologues of the dye rhodamine 6G (R6G and d4-R6G), adsorbed on colloidal Ag particles immobilized in polyvinyl alcohol (PVA). The distributions of pressure-induced blueshifts and linewidths of individual molecules were obtained at different pressures. The linewidth of the single-molecule Raman spectra increased little with pressure, but the variations in blueshifts increased significantly and accounted for most of the pressure-broadening found in the ensemble Raman spectra. To study the pressure effect on plasmon-based electromagnetic enhancement, localized surface plasmon resonance (LSPR) spectra of a photonic substrate and Raman scattering spectra of bezenethiol (BT) monolayers adsorbed upon were measured simultaneously under high pressure. The LSPR split into two peaks under initial compression, and both peaks redshifted with further-increased pressure. The shifts in LSPR was correlated to the Raman intensity variations found in BT Raman spectra. These results suggest that both deformation in the nanoparticles and changes in the dielectric functions with pressure should be taken into account when designing SERS substrates intended for working at high pressures.","Submission published under a 24 month embargo labeled 'U of I only', the embargo will last until 2017-05-01","The student, Yuanxi Fu, accepted the attached license on 2015-03-04 at 15:02.","The student, Yuanxi Fu, submitted this Dissertation for approval on 2015-03-04 at 15:21.","This Dissertation was approved for publication on 2015-03-05 at 15:48.","DSpace SAF Submission Ingestion Package generated from Vireo submission #7735 on 2015-07-22 at 14:16:50","Made available in DSpace on 2015-07-22T22:32:54Z (GMT). No. of bitstreams: 3 Fu_Yuanxi12.pdf: 2346644 bytes, checksum: 3b6c55843c94375a0c358a716c5cdcc4 (MD5) Fu_Yuanxi.docx: 2563195 bytes, checksum: 6272fe44cb40f195448877e246400e27 (MD5) license.txt: 4054 bytes, checksum: 1b3cbe182749857739c7c2843432cef7 (MD5) Previous issue date: 2015-03-05","Embargo set by: Seth Robbins for item 79829 Lift date: 2017-07-22T22:34:16Z Reason: Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system","U of I Only Restriction Lifted for Item 79829 on 2017-07-23T09:15:24Z."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["High pressure surface enhanced Raman scattering spectroscopy"]}]}],"canonical_facts":{"dc:contributor":["Dlott, Dana","Gruebele, Martin","Bass, Jay D.","Granick, Steve"],"dc:creator":["Fu, Yuanxi"],"dc:date":["2015-07-22T22:32:54Z","2017-07-23T09:15:24Z","2015-05","2015-03-05","2015-5"],"dc:description":["Surface-enhanced Raman scattering spectroscopy (SERS) was combined with the diamond anvil cell technique to study molecular monolayers and single molecules under high pressure. Vibrational spectra up to 8 GPa were obtained for self-assembled monolayers (SAMs) of the energetic material simulant 4-nitrobenzenethiol (NBT). A large pressure-broadening NO2 symmetrical stretch was found in the SAMs but not in solid NBT. Single-molecule Raman spectra were studied at high pressures (1-4 GPa). The molecules were two isotopologues of the dye rhodamine 6G (R6G and d4-R6G), adsorbed on colloidal Ag particles immobilized in polyvinyl alcohol (PVA). The distributions of pressure-induced blueshifts and linewidths of individual molecules were obtained at different pressures. The linewidth of the single-molecule Raman spectra increased little with pressure, but the variations in blueshifts increased significantly and accounted for most of the pressure-broadening found in the ensemble Raman spectra. To study the pressure effect on plasmon-based electromagnetic enhancement, localized surface plasmon resonance (LSPR) spectra of a photonic substrate and Raman scattering spectra of bezenethiol (BT) monolayers adsorbed upon were measured simultaneously under high pressure. The LSPR split into two peaks under initial compression, and both peaks redshifted with further-increased pressure. The shifts in LSPR was correlated to the Raman intensity variations found in BT Raman spectra. These results suggest that both deformation in the nanoparticles and changes in the dielectric functions with pressure should be taken into account when designing SERS substrates intended for working at high pressures.","Submission published under a 24 month embargo labeled 'U of I only', the embargo will last until 2017-05-01","The student, Yuanxi Fu, accepted the attached license on 2015-03-04 at 15:02.","The student, Yuanxi Fu, submitted this Dissertation for approval on 2015-03-04 at 15:21.","This Dissertation was approved for publication on 2015-03-05 at 15:48.","DSpace SAF Submission Ingestion Package generated from Vireo submission #7735 on 2015-07-22 at 14:16:50","Made available in DSpace on 2015-07-22T22:32:54Z (GMT). No. of bitstreams: 3 Fu_Yuanxi12.pdf: 2346644 bytes, checksum: 3b6c55843c94375a0c358a716c5cdcc4 (MD5) Fu_Yuanxi.docx: 2563195 bytes, checksum: 6272fe44cb40f195448877e246400e27 (MD5) license.txt: 4054 bytes, checksum: 1b3cbe182749857739c7c2843432cef7 (MD5) Previous issue date: 2015-03-05","Embargo set by: Seth Robbins for item 79829 Lift date: 2017-07-22T22:34:16Z Reason: Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system","U of I Only Restriction Lifted for Item 79829 on 2017-07-23T09:15:24Z."],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/2142/78588"],"dc:rights":["Copyright 2015 Yuanxi Fu"],"dc:subject":["single-molecule spectroscopy","diamond anvil cell","surface enhanced Raman scattering spectroscopy","High pressure"],"dc:title":["High pressure surface enhanced Raman scattering spectroscopy"],"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":"2026-07-22T22:26:12Z"}