{"id":{"repo_id":"wustl","oai_identifier":"oai:openscholarship.wustl.edu:etd-2295"},"canonical_url":"https://search.dev.ndltd.org/etd/wustl/oai:openscholarship.wustl.edu:etd-2295","repository":{"repo_id":"wustl","name":"Washington University in St. Louis","base_url":"https://openscholarship.wustl.edu/do/oai/"},"display":{"title":"Effects of Anion Excited States on Photodetachment of Negative Ions","abstract":"<p>In this dissertation, effects of anion excited states on photodetachment of negative ions containing transition metals will be presented. Evidence of autodetachment (sudden change in photodetachment cross section and photoelectron agular distribution) is observed for diatomic (AgF<super>-</super>, CuF<super>-</super>) and triatomic (NiO<sub>2</sub><super>-</super>, CuOF<super>-</super>) anions. The mechanism of the autodetachment (vibrational or electronic autodetachment) is explored using ab initio calculation. EOM-CCSD calculation reveals a dipole bound anion state, which is responsible for vibrational autodetachment observed in AgF<super>-</super> detachment. Additionally, CAP/EOM-CCSD calculation and experimental data suggest the presence of shape resonances ([AgF<super>-</super>]* and [CuF<super>-</super>]*) which electronically autodetach to several vibrational levels of the ground state. In addition to autodetachment, photodissociation from an anion excited state is also studied. Power dependent photodetachment studies of CuO<sub>2</sub><super>-</super> reveals a two photon Cu<super>-</super> signal for which the only isomer produced (linear OCuO<super>-</super>) is responsible. The dissociation pathway involves a long-lived anion excited state which is stable to electron loss but unstable to dissociation.</p>","abstract_html":"&lt;p&gt;In this dissertation, effects of anion excited states on photodetachment of negative ions containing transition metals will be presented. Evidence of autodetachment (sudden change in photodetachment cross section and photoelectron agular distribution) is observed for diatomic (AgF&lt;super&gt;-&lt;/super&gt;, CuF&lt;super&gt;-&lt;/super&gt;) and triatomic (NiO&lt;sub&gt;2&lt;/sub&gt;&lt;super&gt;-&lt;/super&gt;, CuOF&lt;super&gt;-&lt;/super&gt;) anions. The mechanism of the autodetachment (vibrational or electronic autodetachment) is explored using ab initio calculation. EOM-CCSD calculation reveals a dipole bound anion state, which is responsible for vibrational autodetachment observed in AgF&lt;super&gt;-&lt;/super&gt; detachment. Additionally, CAP/EOM-CCSD calculation and experimental data suggest the presence of shape resonances ([AgF&lt;super&gt;-&lt;/super&gt;]* and [CuF&lt;super&gt;-&lt;/super&gt;]*) which electronically autodetach to several vibrational levels of the ground state. In addition to autodetachment, photodissociation from an anion excited state is also studied. Power dependent photodetachment studies of CuO&lt;sub&gt;2&lt;/sub&gt;&lt;super&gt;-&lt;/super&gt; reveals a two photon Cu&lt;super&gt;-&lt;/super&gt; signal for which the only isomer produced (linear OCuO&lt;super&gt;-&lt;/super&gt;) is responsible. The dissociation pathway involves a long-lived anion excited state which is stable to electron loss but unstable to dissociation.&lt;/p&gt;","abstract_has_math":false,"creators":["Dao, Diep"],"institution":null,"degree_name":"Doctor of Philosophy (PhD)","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Richard Mabbs"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-09-01T07:00:00Z","date_published":"2014-09-01T07:00:00Z","updated_at":"2026-07-24T06:12:32Z","subjects":["anion","autodetachment","dipole bound state","photodetachment","photoelectron imaging","resonances"],"languages":["English (en)"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.doi","label":"DOI","values":["https://doi.org/10.7936/K70P0X3N"],"render_values":[{"text":"https://doi.org/10.7936/K70P0X3N","href":"https://doi.org/10.7936/K70P0X3N","code":true}]}]},"links":{"outbound_url":"https://openscholarship.wustl.edu/etd/1295","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Richard Mabbs"]},{"key":"dc:creator","label":"Author","values":["Dao, Diep"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["2014-10-08T07:00:00Z"]},{"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":["Doctor of Philosophy (PhD)"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["anion","autodetachment","dipole bound state","photodetachment","photoelectron imaging","resonances"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["English (en)"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://openscholarship.wustl.edu/etd/1295"]},{"key":"dc:identifier.doi","label":"DOI","values":["https://doi.org/10.7936/K70P0X3N"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["<p>In this dissertation, effects of anion excited states on photodetachment of negative ions containing transition metals will be presented. Evidence of autodetachment (sudden change in photodetachment cross section and photoelectron agular distribution) is observed for diatomic (AgF<super>-</super>, CuF<super>-</super>) and triatomic (NiO<sub>2</sub><super>-</super>, CuOF<super>-</super>) anions. The mechanism of the autodetachment (vibrational or electronic autodetachment) is explored using ab initio calculation. EOM-CCSD calculation reveals a dipole bound anion state, which is responsible for vibrational autodetachment observed in AgF<super>-</super> detachment. Additionally, CAP/EOM-CCSD calculation and experimental data suggest the presence of shape resonances ([AgF<super>-</super>]* and [CuF<super>-</super>]*) which electronically autodetach to several vibrational levels of the ground state. In addition to autodetachment, photodissociation from an anion excited state is also studied. Power dependent photodetachment studies of CuO<sub>2</sub><super>-</super> reveals a two photon Cu<super>-</super> signal for which the only isomer produced (linear OCuO<super>-</super>) is responsible. The dissociation pathway involves a long-lived anion excited state which is stable to electron loss but unstable to dissociation.</p>"]},{"key":"dc:title","label":"Title","values":["Effects of Anion Excited States on Photodetachment of Negative Ions"]}]}],"canonical_facts":{"dc:contributor":["Richard Mabbs"],"dc:creator":["Dao, Diep"],"dc:date.available":["2014-10-08T07:00:00Z"],"dc:description.abstract":["<p>In this dissertation, effects of anion excited states on photodetachment of negative ions containing transition metals will be presented. Evidence of autodetachment (sudden change in photodetachment cross section and photoelectron agular distribution) is observed for diatomic (AgF<super>-</super>, CuF<super>-</super>) and triatomic (NiO<sub>2</sub><super>-</super>, CuOF<super>-</super>) anions. The mechanism of the autodetachment (vibrational or electronic autodetachment) is explored using ab initio calculation. EOM-CCSD calculation reveals a dipole bound anion state, which is responsible for vibrational autodetachment observed in AgF<super>-</super> detachment. Additionally, CAP/EOM-CCSD calculation and experimental data suggest the presence of shape resonances ([AgF<super>-</super>]* and [CuF<super>-</super>]*) which electronically autodetach to several vibrational levels of the ground state. In addition to autodetachment, photodissociation from an anion excited state is also studied. Power dependent photodetachment studies of CuO<sub>2</sub><super>-</super> reveals a two photon Cu<super>-</super> signal for which the only isomer produced (linear OCuO<super>-</super>) is responsible. The dissociation pathway involves a long-lived anion excited state which is stable to electron loss but unstable to dissociation.</p>"],"dc:identifier":["https://openscholarship.wustl.edu/etd/1295"],"dc:identifier.doi":["https://doi.org/10.7936/K70P0X3N"],"dc:language":["English (en)"],"dc:subject":["anion","autodetachment","dipole bound state","photodetachment","photoelectron imaging","resonances"],"dc:title":["Effects of Anion Excited States on Photodetachment of Negative Ions"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Doctor of Philosophy (PhD)"]},"updated_at":"2026-07-24T06:12:32Z"}