{"id":{"repo_id":"alabama","oai_identifier":"oai:ir.ua.edu:123456789/8582"},"canonical_url":"https://search.dev.ndltd.org/etd/alabama/oai:ir.ua.edu:123456789/8582","repository":{"repo_id":"alabama","name":"University of Alabama","base_url":"https://ir-api.ua.edu/oai/request"},"display":{"title":"An Exploration of Bonding in V_1−x Mo_x O_2 (x ≤ 0.53) and Other Compounds","abstract":"Transition metal solid-state compounds have received much attention due to their vast array of novel functional properties. However, their use is often impeded by an insufficient understanding of the structure-property relationship. This dissertation examines bonding in two families of transition metal compounds to elucidate connections to their electronic properties, V\\(_{1-x}\\)Mo\\(_{x}\\)O\\(_2\\) and ZrSi. The primary focus was to understand the effects of strong metal--metal bonding on the structural disorder in V\\(_{1-x}\\)Mo\\(_{x}\\)O\\(_2\\), using a detailed analysis of total x-ray scattering data. This investigation established that strong metal--metal bonding enhances short-range correlations in the rutile phase while suppressing long-range correlations in the low-temperature phases, which is also accompanied by the suppression of the transition temperature and magnitude of the lattice anomaly. Together, these findings indicate that the disruption of long-range three-dimensional order can now be seen as the result of geometric frustration. This explains VO\\(_2\\)'s negative lattice anomaly. The total collapse of long-range three-dimensional order seems to occur around the same concentration that the lattice anomaly switches sign, identifying it as a potential order parameter. This also implies that the M1 phases of VO\\(_2\\) and MoO\\(_2\\) are distinct. The exploration of bonding in ZrSi resulted in a revised crystal structure of \\(\\beta\\)-ZrSi (space group \\(Cmcm\\)) from single-crystal x-ray diffraction data, correcting the atomic position and bond distances. The revised Si--Si bond length has been modified substantially from 2.723(6) Å to 2.4411(8) Å. Additionally, a comprehensive analysis of bonding trends in early transition metal compounds closely related to FeB-type \\(\\alpha\\)-ZrSi and CrB-type \\(\\beta\\)-ZrSi was completed, using electronic structures calculated by the Linear Muffin-Tin Orbital (LMTO) method.","abstract_html":"Transition metal solid-state compounds have received much attention due to their vast array of novel functional properties. However, their use is often impeded by an insufficient understanding of the structure-property relationship. This dissertation examines bonding in two families of transition metal compounds to elucidate connections to their electronic properties, V<span class=\"etd-inline-math\"><sub>1-x</sub></span>Mo<span class=\"etd-inline-math\"><sub>x</sub></span>O<span class=\"etd-inline-math\"><sub>2</sub></span> and ZrSi. The primary focus was to understand the effects of strong metal--metal bonding on the structural disorder in V<span class=\"etd-inline-math\"><sub>1-x</sub></span>Mo<span class=\"etd-inline-math\"><sub>x</sub></span>O<span class=\"etd-inline-math\"><sub>2</sub></span>, using a detailed analysis of total x-ray scattering data. This investigation established that strong metal--metal bonding enhances short-range correlations in the rutile phase while suppressing long-range correlations in the low-temperature phases, which is also accompanied by the suppression of the transition temperature and magnitude of the lattice anomaly. Together, these findings indicate that the disruption of long-range three-dimensional order can now be seen as the result of geometric frustration. This explains VO<span class=\"etd-inline-math\"><sub>2</sub></span>&#x27;s negative lattice anomaly. The total collapse of long-range three-dimensional order seems to occur around the same concentration that the lattice anomaly switches sign, identifying it as a potential order parameter. This also implies that the M1 phases of VO<span class=\"etd-inline-math\"><sub>2</sub></span> and MoO<span class=\"etd-inline-math\"><sub>2</sub></span> are distinct. The exploration of bonding in ZrSi resulted in a revised crystal structure of <span class=\"etd-inline-math\">&beta;</span>-ZrSi (space group \\(Cmcm\\)) from single-crystal x-ray diffraction data, correcting the atomic position and bond distances. The revised Si--Si bond length has been modified substantially from 2.723(6) Å to 2.4411(8) Å. Additionally, a comprehensive analysis of bonding trends in early transition metal compounds closely related to FeB-type <span class=\"etd-inline-math\">&alpha;</span>-ZrSi and CrB-type <span class=\"etd-inline-math\">&beta;</span>-ZrSi was completed, using electronic structures calculated by the Linear Muffin-Tin Orbital (LMTO) method.","abstract_has_math":true,"creators":["Douglas, Tyra"],"institution":"University of Alabama Libraries","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Gupta, Arunava","Szulczewski, Gregory J","Rupar, Paul A","Weaver, Mark L"],"advisors":["Allred, Jared M."],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022","date_published":"2022","updated_at":"2026-07-27T18:44:25Z","subjects":[],"languages":["en_US","English"],"rights":["All rights reserved by the author unless otherwise indicated."],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["http://purl.lib.ua.edu/184315","u0015_0000001_0004364","Douglas_alatus_0004D_14729"],"render_values":[{"text":"http://purl.lib.ua.edu/184315","href":"http://purl.lib.ua.edu/184315","code":true},{"text":"u0015_0000001_0004364","href":null,"code":true},{"text":"Douglas_alatus_0004D_14729","href":null,"code":true}]}]},"links":{"outbound_url":"https://ir.ua.edu/handle/123456789/8582","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Gupta, Arunava","Szulczewski, Gregory J","Rupar, Paul A","Weaver, Mark L"]},{"key":"dc:contributor.advisor","label":"Advisor","values":["Allred, Jared M."]},{"key":"dc:contributor.other","label":"Dc Contributor Other","values":["University of Alabama Tuscaloosa"]},{"key":"dc:creator","label":"Author","values":["Douglas, Tyra"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2022-07-05T20:07:34Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2022-07-05T20:07:34Z"]},{"key":"dc:date.issued","label":"Date","values":["2022"]},{"key":"dc:publisher","label":"Institution","values":["University of Alabama Libraries"]},{"key":"dc:type","label":"Dc Type","values":["thesis","text"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["English"]},{"key":"dc:language.iso","label":"Language (ISO)","values":["en_US"]},{"key":"dc:rights","label":"Dc Rights","values":["All rights reserved by the author unless otherwise indicated."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["http://purl.lib.ua.edu/184315","u0015_0000001_0004364","Douglas_alatus_0004D_14729"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://ir.ua.edu/handle/123456789/8582"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Electronic Thesis or Dissertation"]},{"key":"dc:description.abstract","label":"Abstract","values":["Transition metal solid-state compounds have received much attention due to their vast array of novel functional properties. However, their use is often impeded by an insufficient understanding of the structure-property relationship. This dissertation examines bonding in two families of transition metal compounds to elucidate connections to their electronic properties, V\\(_{1-x}\\)Mo\\(_{x}\\)O\\(_2\\) and ZrSi. The primary focus was to understand the effects of strong metal--metal bonding on the structural disorder in V\\(_{1-x}\\)Mo\\(_{x}\\)O\\(_2\\), using a detailed analysis of total x-ray scattering data. This investigation established that strong metal--metal bonding enhances short-range correlations in the rutile phase while suppressing long-range correlations in the low-temperature phases, which is also accompanied by the suppression of the transition temperature and magnitude of the lattice anomaly. Together, these findings indicate that the disruption of long-range three-dimensional order can now be seen as the result of geometric frustration. This explains VO\\(_2\\)'s negative lattice anomaly. The total collapse of long-range three-dimensional order seems to occur around the same concentration that the lattice anomaly switches sign, identifying it as a potential order parameter. This also implies that the M1 phases of VO\\(_2\\) and MoO\\(_2\\) are distinct. The exploration of bonding in ZrSi resulted in a revised crystal structure of \\(\\beta\\)-ZrSi (space group \\(Cmcm\\)) from single-crystal x-ray diffraction data, correcting the atomic position and bond distances. The revised Si--Si bond length has been modified substantially from 2.723(6) Å to 2.4411(8) Å. Additionally, a comprehensive analysis of bonding trends in early transition metal compounds closely related to FeB-type \\(\\alpha\\)-ZrSi and CrB-type \\(\\beta\\)-ZrSi was completed, using electronic structures calculated by the Linear Muffin-Tin Orbital (LMTO) method."]},{"key":"dc:format.medium","label":"Dc Format Medium","values":["electronic"]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["An Exploration of Bonding in V_1−x Mo_x O_2 (x ≤ 0.53) and Other Compounds"]}]}],"canonical_facts":{"dc:contributor":["Gupta, Arunava","Szulczewski, Gregory J","Rupar, Paul A","Weaver, Mark L"],"dc:contributor.advisor":["Allred, Jared M."],"dc:contributor.other":["University of Alabama Tuscaloosa"],"dc:creator":["Douglas, Tyra"],"dc:date.accessioned":["2022-07-05T20:07:34Z"],"dc:date.available":["2022-07-05T20:07:34Z"],"dc:date.issued":["2022"],"dc:description":["Electronic Thesis or Dissertation"],"dc:description.abstract":["Transition metal solid-state compounds have received much attention due to their vast array of novel functional properties. However, their use is often impeded by an insufficient understanding of the structure-property relationship. This dissertation examines bonding in two families of transition metal compounds to elucidate connections to their electronic properties, V\\(_{1-x}\\)Mo\\(_{x}\\)O\\(_2\\) and ZrSi. The primary focus was to understand the effects of strong metal--metal bonding on the structural disorder in V\\(_{1-x}\\)Mo\\(_{x}\\)O\\(_2\\), using a detailed analysis of total x-ray scattering data. This investigation established that strong metal--metal bonding enhances short-range correlations in the rutile phase while suppressing long-range correlations in the low-temperature phases, which is also accompanied by the suppression of the transition temperature and magnitude of the lattice anomaly. Together, these findings indicate that the disruption of long-range three-dimensional order can now be seen as the result of geometric frustration. This explains VO\\(_2\\)'s negative lattice anomaly. The total collapse of long-range three-dimensional order seems to occur around the same concentration that the lattice anomaly switches sign, identifying it as a potential order parameter. This also implies that the M1 phases of VO\\(_2\\) and MoO\\(_2\\) are distinct. The exploration of bonding in ZrSi resulted in a revised crystal structure of \\(\\beta\\)-ZrSi (space group \\(Cmcm\\)) from single-crystal x-ray diffraction data, correcting the atomic position and bond distances. The revised Si--Si bond length has been modified substantially from 2.723(6) Å to 2.4411(8) Å. Additionally, a comprehensive analysis of bonding trends in early transition metal compounds closely related to FeB-type \\(\\alpha\\)-ZrSi and CrB-type \\(\\beta\\)-ZrSi was completed, using electronic structures calculated by the Linear Muffin-Tin Orbital (LMTO) method."],"dc:format.medium":["electronic"],"dc:format.mimetype":["application/pdf"],"dc:identifier.other":["http://purl.lib.ua.edu/184315","u0015_0000001_0004364","Douglas_alatus_0004D_14729"],"dc:identifier.uri":["https://ir.ua.edu/handle/123456789/8582"],"dc:language":["English"],"dc:language.iso":["en_US"],"dc:publisher":["University of Alabama Libraries"],"dc:rights":["All rights reserved by the author unless otherwise indicated."],"dc:title":["An Exploration of Bonding in V_1−x Mo_x O_2 (x ≤ 0.53) and Other Compounds"],"dc:type":["thesis","text"]},"updated_at":"2026-07-27T18:44:25Z"}