{"id":{"repo_id":"cornell","oai_identifier":"oai:ecommons.cornell.edu:1813/56870"},"canonical_url":"https://search.dev.ndltd.org/etd/cornell/oai:ecommons.cornell.edu:1813/56870","repository":{"repo_id":"cornell","name":"Cornell University","base_url":"https://ecommons.cornell.edu/server/oai/request"},"display":{"title":"Understanding the Vibrational Features of Hydrogen-Bonded Dimers","abstract":"Hydrogen-bonded systems often exhibit very broad and unusually shaped features in their vibrational spectra. The origin of these features is oftentimes unclear. Consequently, computational methods are frequently used to model these features in order to better understand their origin. However, reproducing these features with computational methods is often quite challenging. Many methods have been developed each of which has its own advantages and disadvantages. The research presented in this thesis focuses on the development and application of new computational methods to reproduce the multi-hump (broad peak) vibrational features found in many hydrogen-bonded dimers. These methods utilize density functional theory to calculate the potential energy surface and a quantum variational approach to calculate vibrational spectra from these surfaces. One of the methods developed involves adiabatically separating lower frequency vibrational modes, which modulate the hydrogen bond length, from higher frequency modes that contribute to the structure. Another method that was developed uses a classical molecular dynamics simulation, in place of low-frequency modes, to more accurately sample configurations. The results of the calculations performed with these methods indicate that the broadness of these multi-hump features originate from low-frequency modes modulating the hydrogen bond length, while the multi-hump lineshape is derived from strong Fermi resonances between the OH stretch and the OH bending modes.","abstract_html":"Hydrogen-bonded systems often exhibit very broad and unusually shaped features in their vibrational spectra. The origin of these features is oftentimes unclear. Consequently, computational methods are frequently used to model these features in order to better understand their origin. However, reproducing these features with computational methods is often quite challenging. Many methods have been developed each of which has its own advantages and disadvantages. The research presented in this thesis focuses on the development and application of new computational methods to reproduce the multi-hump (broad peak) vibrational features found in many hydrogen-bonded dimers. These methods utilize density functional theory to calculate the potential energy surface and a quantum variational approach to calculate vibrational spectra from these surfaces. One of the methods developed involves adiabatically separating lower frequency vibrational modes, which modulate the hydrogen bond length, from higher frequency modes that contribute to the structure. Another method that was developed uses a classical molecular dynamics simulation, in place of low-frequency modes, to more accurately sample configurations. The results of the calculations performed with these methods indicate that the broadness of these multi-hump features originate from low-frequency modes modulating the hydrogen bond length, while the multi-hump lineshape is derived from strong Fermi resonances between the OH stretch and the OH bending modes.","abstract_has_math":false,"creators":["Van Hoozen, Brian Lynn"],"institution":"Cornell University","degree_name":"Ph. D., Chemistry and Chemical Biology","degree_level":"Doctor of Philosophy","degree_discipline":"Chemistry and Chemical Biology","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":["Ezra, Gregory Sion","Davis, Harry Floyd"],"year":2017,"date_issued":"2017-08-30","date_published":"2017-08-30","updated_at":"2026-07-24T01:49:08Z","subjects":["density functional theory","Physical chemistry","Computational Chemistry","Dimers","Hydrogen Bonding","Infrared Spectroscopy"],"languages":["en_US"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.doi","label":"DOI","values":["https://doi.org/10.7298/X43X84SH"],"render_values":[{"text":"https://doi.org/10.7298/X43X84SH","href":"https://doi.org/10.7298/X43X84SH","code":true}]},{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["ProQuest Submission ID: 10355","ProQuest Publication ID: 10602739"],"render_values":[{"text":"ProQuest Submission ID: 10355","href":null,"code":true},{"text":"ProQuest Publication ID: 10602739","href":null,"code":true}]}]},"links":{"outbound_url":"https://hdl.handle.net/1813/56870","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.committeemember","label":"Committee Member","values":["Ezra, Gregory Sion","Davis, Harry Floyd"]},{"key":"dc:creator","label":"Author","values":["Van Hoozen, Brian Lynn"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2018-04-26T14:17:02Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2018-09-11T06:00:36Z"]},{"key":"dc:date.issued","label":"Date","values":["2017-08-30"]},{"key":"dc:type","label":"Dc Type","values":["dissertation or thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry and Chemical Biology"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Doctor of Philosophy"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph. 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The origin of these features is oftentimes unclear. Consequently, computational methods are frequently used to model these features in order to better understand their origin. However, reproducing these features with computational methods is often quite challenging. Many methods have been developed each of which has its own advantages and disadvantages. The research presented in this thesis focuses on the development and application of new computational methods to reproduce the multi-hump (broad peak) vibrational features found in many hydrogen-bonded dimers. These methods utilize density functional theory to calculate the potential energy surface and a quantum variational approach to calculate vibrational spectra from these surfaces. One of the methods developed involves adiabatically separating lower frequency vibrational modes, which modulate the hydrogen bond length, from higher frequency modes that contribute to the structure. Another method that was developed uses a classical molecular dynamics simulation, in place of low-frequency modes, to more accurately sample configurations. The results of the calculations performed with these methods indicate that the broadness of these multi-hump features originate from low-frequency modes modulating the hydrogen bond length, while the multi-hump lineshape is derived from strong Fermi resonances between the OH stretch and the OH bending modes."]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Understanding the Vibrational Features of Hydrogen-Bonded Dimers"]}]}],"canonical_facts":{"dc:contributor.committeemember":["Ezra, Gregory Sion","Davis, Harry Floyd"],"dc:creator":["Van Hoozen, Brian Lynn"],"dc:date.accessioned":["2018-04-26T14:17:02Z"],"dc:date.available":["2018-09-11T06:00:36Z"],"dc:date.issued":["2017-08-30"],"dc:description.abstract":["Hydrogen-bonded systems often exhibit very broad and unusually shaped features in their vibrational spectra. The origin of these features is oftentimes unclear. Consequently, computational methods are frequently used to model these features in order to better understand their origin. However, reproducing these features with computational methods is often quite challenging. Many methods have been developed each of which has its own advantages and disadvantages. The research presented in this thesis focuses on the development and application of new computational methods to reproduce the multi-hump (broad peak) vibrational features found in many hydrogen-bonded dimers. These methods utilize density functional theory to calculate the potential energy surface and a quantum variational approach to calculate vibrational spectra from these surfaces. One of the methods developed involves adiabatically separating lower frequency vibrational modes, which modulate the hydrogen bond length, from higher frequency modes that contribute to the structure. Another method that was developed uses a classical molecular dynamics simulation, in place of low-frequency modes, to more accurately sample configurations. The results of the calculations performed with these methods indicate that the broadness of these multi-hump features originate from low-frequency modes modulating the hydrogen bond length, while the multi-hump lineshape is derived from strong Fermi resonances between the OH stretch and the OH bending modes."],"dc:format.mimetype":["application/pdf"],"dc:identifier.doi":["https://doi.org/10.7298/X43X84SH"],"dc:identifier.other":["ProQuest Submission ID: 10355","ProQuest Publication ID: 10602739"],"dc:identifier.uri":["https://hdl.handle.net/1813/56870"],"dc:language.iso":["en_US"],"dc:subject":["density functional theory","Physical chemistry","Computational Chemistry","Dimers","Hydrogen Bonding","Infrared Spectroscopy"],"dc:title":["Understanding the Vibrational Features of Hydrogen-Bonded Dimers"],"dc:type":["dissertation or thesis"],"thesis:degree_discipline":["Chemistry and Chemical Biology"],"thesis:degree_level":["Doctor of Philosophy"],"thesis:degree_name":["Ph. 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