{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/106433"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/106433","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Development of non-born-Oppenheimer methods for ground and excited state molecular properties","abstract":"The nuclear-electronic orbital (NEO) method is a multicomponent approach that allows the quantum mechanical treatment of electrons and specified protons on the same quantum mechanical level. NEO does not make the Born-Oppenheimber approximation between electrons and select protons, and therefore has great potential in applications to non-Born-Oppenheimer processes such as proton-coupled electron transfer (PCET). Additionally, NEO can also capture nuclear quantum effects such as zero-point energy and proton delocalization in a direct and efficient manner. This dissertation describes the development of NEO methods for calculating both ground and excited state molecular properties. For the ground state, a general multicomponent embedding scheme is developed and tested within the NEO framework to obtain nuclear densities. Machinery is also presented for identifying the character and stability of NEO self-consistent field (SCF) solutions, allowing the differentiation between minima and saddle points. For excited states, the linear response multicomponent time-dependent density functional theory (TDDFT) is derived and implemented within the NEO framework. The results for nuclear vibrational excitations of interest corresponding to single or multiple protons calculated with NEO-TDDFT are accurate when the method is used in conjunction with large nuclear and electronic basis sets. Lastly, a scheme is presented for coupling proton vibrational excitation energies calculated with NEO-TDDFT to the normal modes associated with the other nuclei. This scheme, denoted NEO-DFT(V), thereby allows for full molecular vibrational frequencies to be calculated. These NEO methods provide the foundation for a wide range of applications, especially those involving non-Born-Oppenheimber processes or nuclear quantum effects.","abstract_html":"The nuclear-electronic orbital (NEO) method is a multicomponent approach that allows the quantum mechanical treatment of electrons and specified protons on the same quantum mechanical level. NEO does not make the Born-Oppenheimber approximation between electrons and select protons, and therefore has great potential in applications to non-Born-Oppenheimer processes such as proton-coupled electron transfer (PCET). Additionally, NEO can also capture nuclear quantum effects such as zero-point energy and proton delocalization in a direct and efficient manner. This dissertation describes the development of NEO methods for calculating both ground and excited state molecular properties. For the ground state, a general multicomponent embedding scheme is developed and tested within the NEO framework to obtain nuclear densities. Machinery is also presented for identifying the character and stability of NEO self-consistent field (SCF) solutions, allowing the differentiation between minima and saddle points. For excited states, the linear response multicomponent time-dependent density functional theory (TDDFT) is derived and implemented within the NEO framework. The results for nuclear vibrational excitations of interest corresponding to single or multiple protons calculated with NEO-TDDFT are accurate when the method is used in conjunction with large nuclear and electronic basis sets. Lastly, a scheme is presented for coupling proton vibrational excitation energies calculated with NEO-TDDFT to the normal modes associated with the other nuclei. This scheme, denoted NEO-DFT(V), thereby allows for full molecular vibrational frequencies to be calculated. These NEO methods provide the foundation for a wide range of applications, especially those involving non-Born-Oppenheimber processes or nuclear quantum effects.","abstract_has_math":false,"creators":["Culpitt, Tanner P."],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Hammes-Schiffer, Sharon","Makri, Nancy","Vura-Weis, Joshua","Wagner, Lucas"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2020,"date_issued":"2020-03-02T22:38:39Z","date_published":"2020-03-02T22:38:39Z","updated_at":"2026-07-22T22:24:47Z","subjects":["electronic structure","non-Born-Oppenheimer","DFT","TDDFT","Wave Function"],"languages":["en"],"rights":["Copyright 2019 Tanner Culpitt"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/106433","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Hammes-Schiffer, Sharon","Makri, Nancy","Vura-Weis, Joshua","Wagner, Lucas"]},{"key":"dc:creator","label":"Author","values":["Culpitt, Tanner P."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2020-03-02T22:38:39Z","2022-03-03T10:15:30Z","2019-10-17","2019-12"]},{"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":["electronic structure","non-Born-Oppenheimer","DFT","TDDFT","Wave Function"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2019 Tanner Culpitt"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/106433"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The nuclear-electronic orbital (NEO) method is a multicomponent approach that allows the quantum mechanical treatment of electrons and specified protons on the same quantum mechanical level. NEO does not make the Born-Oppenheimber approximation between electrons and select protons, and therefore has great potential in applications to non-Born-Oppenheimer processes such as proton-coupled electron transfer (PCET). Additionally, NEO can also capture nuclear quantum effects such as zero-point energy and proton delocalization in a direct and efficient manner. This dissertation describes the development of NEO methods for calculating both ground and excited state molecular properties. For the ground state, a general multicomponent embedding scheme is developed and tested within the NEO framework to obtain nuclear densities. Machinery is also presented for identifying the character and stability of NEO self-consistent field (SCF) solutions, allowing the differentiation between minima and saddle points. For excited states, the linear response multicomponent time-dependent density functional theory (TDDFT) is derived and implemented within the NEO framework. The results for nuclear vibrational excitations of interest corresponding to single or multiple protons calculated with NEO-TDDFT are accurate when the method is used in conjunction with large nuclear and electronic basis sets. Lastly, a scheme is presented for coupling proton vibrational excitation energies calculated with NEO-TDDFT to the normal modes associated with the other nuclei. This scheme, denoted NEO-DFT(V), thereby allows for full molecular vibrational frequencies to be calculated. These NEO methods provide the foundation for a wide range of applications, especially those involving non-Born-Oppenheimber processes or nuclear quantum effects.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2021-12-01","The student, Tanner Culpitt, accepted the attached license on 2019-10-16 at 10:14.","The student, Tanner Culpitt, submitted this Dissertation for approval on 2019-10-16 at 10:14.","This Dissertation was approved for publication on 2019-10-17 at 15:11.","DSpace SAF Submission Ingestion Package generated from Vireo submission #14498 on 2020-02-28 at 17:35:40","Made available in DSpace on 2020-03-02T22:38:39Z (GMT). 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NEO does not make the Born-Oppenheimber approximation between electrons and select protons, and therefore has great potential in applications to non-Born-Oppenheimer processes such as proton-coupled electron transfer (PCET). Additionally, NEO can also capture nuclear quantum effects such as zero-point energy and proton delocalization in a direct and efficient manner. This dissertation describes the development of NEO methods for calculating both ground and excited state molecular properties. For the ground state, a general multicomponent embedding scheme is developed and tested within the NEO framework to obtain nuclear densities. Machinery is also presented for identifying the character and stability of NEO self-consistent field (SCF) solutions, allowing the differentiation between minima and saddle points. For excited states, the linear response multicomponent time-dependent density functional theory (TDDFT) is derived and implemented within the NEO framework. The results for nuclear vibrational excitations of interest corresponding to single or multiple protons calculated with NEO-TDDFT are accurate when the method is used in conjunction with large nuclear and electronic basis sets. Lastly, a scheme is presented for coupling proton vibrational excitation energies calculated with NEO-TDDFT to the normal modes associated with the other nuclei. This scheme, denoted NEO-DFT(V), thereby allows for full molecular vibrational frequencies to be calculated. These NEO methods provide the foundation for a wide range of applications, especially those involving non-Born-Oppenheimber processes or nuclear quantum effects.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2021-12-01","The student, Tanner Culpitt, accepted the attached license on 2019-10-16 at 10:14.","The student, Tanner Culpitt, submitted this Dissertation for approval on 2019-10-16 at 10:14.","This Dissertation was approved for publication on 2019-10-17 at 15:11.","DSpace SAF Submission Ingestion Package generated from Vireo submission #14498 on 2020-02-28 at 17:35:40","Made available in DSpace on 2020-03-02T22:38:39Z (GMT). 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