{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/23027"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/23027","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Infrared spectroscopy and Monte Carlo simulations of gas phase, solvated alkali ions","abstract":"The solvation of the alkali ions Na$\\sp{+}$ and Cs$\\sp{+}$ by methanol has been investigated by gas-phase vibrational spectroscopy and Monte Carlo simulations of small ion clusters: Na(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$, N = 6 to 15 and Cs(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$, N = 4 to 25. The solvated ions, generated by combining a thermionic alkali ion source with a molecular beam source, have considerable amounts of internal energy. The excess energy is dissipated by evaporation. The quasi-stable cluster ions are mass-selected for vibrational predissociation spectroscopy. The spectra are collected using a line-tunable cw-CO$\\sb2$ laser.","abstract_html":"The solvation of the alkali ions Na$\\sp{+}$ and Cs$\\sp{+}$ by methanol has been investigated by gas-phase vibrational spectroscopy and Monte Carlo simulations of small ion clusters: Na(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$, N = 6 to 15 and Cs(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$, N = 4 to 25. The solvated ions, generated by combining a thermionic alkali ion source with a molecular beam source, have considerable amounts of internal energy. The excess energy is dissipated by evaporation. The quasi-stable cluster ions are mass-selected for vibrational predissociation spectroscopy. The spectra are collected using a line-tunable cw-CO$\\sb2$ laser.","abstract_has_math":true,"creators":["Draves, Jeffrey Albert"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Lisy, James M."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T13:59:33Z","date_published":"2011-05-07T13:59:33Z","updated_at":"2026-07-22T22:25:21Z","subjects":["Chemistry, Physical"],"languages":["eng"],"rights":["Copyright 1990 Draves, Jeffrey Albert"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9114225","(UMI)AAI9114225"],"render_values":[{"text":"AAI9114225","href":null,"code":true},{"text":"(UMI)AAI9114225","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/23027","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Lisy, James M."]},{"key":"dc:creator","label":"Author","values":["Draves, Jeffrey Albert"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:59:33Z","10000-01-01","1990"]},{"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, Physical"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1990 Draves, Jeffrey Albert"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9114225","(UMI)AAI9114225","http://hdl.handle.net/2142/23027"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The solvation of the alkali ions Na$\\sp{+}$ and Cs$\\sp{+}$ by methanol has been investigated by gas-phase vibrational spectroscopy and Monte Carlo simulations of small ion clusters: Na(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$, N = 6 to 15 and Cs(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$, N = 4 to 25. The solvated ions, generated by combining a thermionic alkali ion source with a molecular beam source, have considerable amounts of internal energy. The excess energy is dissipated by evaporation. The quasi-stable cluster ions are mass-selected for vibrational predissociation spectroscopy. The spectra are collected using a line-tunable cw-CO$\\sb2$ laser.","Vibrational spectra indicate that the first solvation shell about the Na$\\sp{+}$ consists of six methanols while that about the Cs$\\sp{+}$ consists of ten. Large clusters of Cs(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$ (N $\\geq$ 18) appear to have small clusters of methanol bound to the surface of the solvated ion. Na(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$ clusters appear to have two structurally enhanced regions, i.e. a first and a second solvation shell.","Monte Carlo simulations using pairwise interaction potentials were run at temperatures between 200 K and 300 K for the solvated ions Na(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$, N = 6-8, 10, 12, 15, and 25, and for Cs(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$, N = 6-16, and 25. Simulation results show the first solvation shell of Na$\\sp{+}$ and Cs$\\sp{+}$ is filled by 6.2 and 10.5 methanols, respectively. These numbers are consistent with experimental results. The simulations also indicate that hydrogen bonding plays a significant role in shaping the solvent shell structure for both species.","Once the first solvation shell is filled, the size of the solvent shell appears to be independent of additional solvent molecules. After N = 6 for Na(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$, and N = 10 for Cs(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$ methanols begin entering the second solvent region, this shell is not filled before methanols enter the third solvent region. This is an indication of the extent to which the ion influences the solvating methanols.","Gas-phase solvated ions appear to be useful models for dilute electolyte solutions. This technique produces solvated ions which exhibit several solvent regions. With the combination of the Monte Carlo simulations and vibrational spectroscopy, a clear picture of the solvation shell structure can be obtained.","Made available in DSpace on 2011-05-07T13:59:33Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9114225.pdf: 5415097 bytes, checksum: ae78ded060cbe2cde5519b38f2044405 (MD5) Previous issue date: 1990","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:01:41Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:29:16-05:00 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":["Infrared spectroscopy and Monte Carlo simulations of gas phase, solvated alkali ions"]}]}],"canonical_facts":{"dc:contributor":["Lisy, James M."],"dc:creator":["Draves, Jeffrey Albert"],"dc:date":["2011-05-07T13:59:33Z","10000-01-01","1990"],"dc:description":["The solvation of the alkali ions Na$\\sp{+}$ and Cs$\\sp{+}$ by methanol has been investigated by gas-phase vibrational spectroscopy and Monte Carlo simulations of small ion clusters: Na(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$, N = 6 to 15 and Cs(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$, N = 4 to 25. The solvated ions, generated by combining a thermionic alkali ion source with a molecular beam source, have considerable amounts of internal energy. The excess energy is dissipated by evaporation. The quasi-stable cluster ions are mass-selected for vibrational predissociation spectroscopy. The spectra are collected using a line-tunable cw-CO$\\sb2$ laser.","Vibrational spectra indicate that the first solvation shell about the Na$\\sp{+}$ consists of six methanols while that about the Cs$\\sp{+}$ consists of ten. Large clusters of Cs(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$ (N $\\geq$ 18) appear to have small clusters of methanol bound to the surface of the solvated ion. Na(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$ clusters appear to have two structurally enhanced regions, i.e. a first and a second solvation shell.","Monte Carlo simulations using pairwise interaction potentials were run at temperatures between 200 K and 300 K for the solvated ions Na(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$, N = 6-8, 10, 12, 15, and 25, and for Cs(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$, N = 6-16, and 25. Simulation results show the first solvation shell of Na$\\sp{+}$ and Cs$\\sp{+}$ is filled by 6.2 and 10.5 methanols, respectively. These numbers are consistent with experimental results. The simulations also indicate that hydrogen bonding plays a significant role in shaping the solvent shell structure for both species.","Once the first solvation shell is filled, the size of the solvent shell appears to be independent of additional solvent molecules. After N = 6 for Na(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$, and N = 10 for Cs(CH$\\sb3$OH) $\\sbsp{\\rm N}{+}$ methanols begin entering the second solvent region, this shell is not filled before methanols enter the third solvent region. This is an indication of the extent to which the ion influences the solvating methanols.","Gas-phase solvated ions appear to be useful models for dilute electolyte solutions. This technique produces solvated ions which exhibit several solvent regions. With the combination of the Monte Carlo simulations and vibrational spectroscopy, a clear picture of the solvation shell structure can be obtained.","Made available in DSpace on 2011-05-07T13:59:33Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9114225.pdf: 5415097 bytes, checksum: ae78ded060cbe2cde5519b38f2044405 (MD5) Previous issue date: 1990","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:01:41Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:29:16-05:00 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":["AAI9114225","(UMI)AAI9114225","http://hdl.handle.net/2142/23027"],"dc:language":["eng"],"dc:rights":["Copyright 1990 Draves, Jeffrey Albert"],"dc:subject":["Chemistry, Physical"],"dc:title":["Infrared spectroscopy and Monte Carlo simulations of gas phase, solvated alkali ions"],"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":"2026-07-22T22:25:21Z"}