{"title":"MoO2多晶金属到半导体转变的密度泛函理论研究","authors":"Adilmo F. Lima","doi":"10.1016/j.cocom.2025.e01137","DOIUrl":null,"url":null,"abstract":"<div><div>Molybdenum dioxide (MoO<sub>2</sub>) has attracted increasing interest due to its potential applications in catalysis, energy storage, and electronic devices. Several theoretical polymorphs have been predicted for this material, but their fundamental properties remain underexplored. In this work, we present a comprehensive density functional theory (DFT) investigation of the structural, magnetic, electronic, and optical properties of three MoO<sub>2</sub> polymorphs (monoclinic (<em>P2</em><sub><em>1</em></sub><em>/c),</em> tetragonal (<em>P4</em><sub><em>2</em></sub><em>/mnm</em>), and hexagonal (<em>P6</em><sub><em>3</em></sub><em>/mmc</em>)) with particular emphasis on the paramagnetic-to-antiferromagnetic and metallic-to-semiconductor transitions. The DFT calculations were conducted using different approximations for the exchange-correlation functional. The spin-polarized calculations indicate that all three phases are non-magnetic. Band structure analyses reveal that while the monoclinic and tetragonal phases remain metallic, the hexagonal polymorph exhibits an indirect band gap of 0.635 eV, indicating a metallic-to-semiconductor transition driven by local structural ordering of the Mo 4d states. The calculated linear optical properties further support these findings, which confirms the reliability of our theoretical approach. Overall, these results provide valuable insights that can guide future investigations of phase transitions in MoO<sub>2</sub> and their potential impact on practical applications in advanced technologies.</div></div>","PeriodicalId":46322,"journal":{"name":"Computational Condensed Matter","volume":"45 ","pages":"Article e01137"},"PeriodicalIF":3.9000,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Density functional theory investigation of the metallic-to-semiconductor transition in MoO2 polymorphs\",\"authors\":\"Adilmo F. Lima\",\"doi\":\"10.1016/j.cocom.2025.e01137\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Molybdenum dioxide (MoO<sub>2</sub>) has attracted increasing interest due to its potential applications in catalysis, energy storage, and electronic devices. Several theoretical polymorphs have been predicted for this material, but their fundamental properties remain underexplored. In this work, we present a comprehensive density functional theory (DFT) investigation of the structural, magnetic, electronic, and optical properties of three MoO<sub>2</sub> polymorphs (monoclinic (<em>P2</em><sub><em>1</em></sub><em>/c),</em> tetragonal (<em>P4</em><sub><em>2</em></sub><em>/mnm</em>), and hexagonal (<em>P6</em><sub><em>3</em></sub><em>/mmc</em>)) with particular emphasis on the paramagnetic-to-antiferromagnetic and metallic-to-semiconductor transitions. The DFT calculations were conducted using different approximations for the exchange-correlation functional. The spin-polarized calculations indicate that all three phases are non-magnetic. Band structure analyses reveal that while the monoclinic and tetragonal phases remain metallic, the hexagonal polymorph exhibits an indirect band gap of 0.635 eV, indicating a metallic-to-semiconductor transition driven by local structural ordering of the Mo 4d states. The calculated linear optical properties further support these findings, which confirms the reliability of our theoretical approach. Overall, these results provide valuable insights that can guide future investigations of phase transitions in MoO<sub>2</sub> and their potential impact on practical applications in advanced technologies.</div></div>\",\"PeriodicalId\":46322,\"journal\":{\"name\":\"Computational Condensed Matter\",\"volume\":\"45 \",\"pages\":\"Article e01137\"},\"PeriodicalIF\":3.9000,\"publicationDate\":\"2025-09-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Computational Condensed Matter\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2352214325001376\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"PHYSICS, CONDENSED MATTER\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Computational Condensed Matter","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2352214325001376","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"PHYSICS, CONDENSED MATTER","Score":null,"Total":0}
Density functional theory investigation of the metallic-to-semiconductor transition in MoO2 polymorphs
Molybdenum dioxide (MoO2) has attracted increasing interest due to its potential applications in catalysis, energy storage, and electronic devices. Several theoretical polymorphs have been predicted for this material, but their fundamental properties remain underexplored. In this work, we present a comprehensive density functional theory (DFT) investigation of the structural, magnetic, electronic, and optical properties of three MoO2 polymorphs (monoclinic (P21/c), tetragonal (P42/mnm), and hexagonal (P63/mmc)) with particular emphasis on the paramagnetic-to-antiferromagnetic and metallic-to-semiconductor transitions. The DFT calculations were conducted using different approximations for the exchange-correlation functional. The spin-polarized calculations indicate that all three phases are non-magnetic. Band structure analyses reveal that while the monoclinic and tetragonal phases remain metallic, the hexagonal polymorph exhibits an indirect band gap of 0.635 eV, indicating a metallic-to-semiconductor transition driven by local structural ordering of the Mo 4d states. The calculated linear optical properties further support these findings, which confirms the reliability of our theoretical approach. Overall, these results provide valuable insights that can guide future investigations of phase transitions in MoO2 and their potential impact on practical applications in advanced technologies.