Density functional theory investigation of the metallic-to-semiconductor transition in MoO2 polymorphs

IF 3.9 Q3 PHYSICS, CONDENSED MATTER
Adilmo F. Lima
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Abstract

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.

Abstract Image

MoO2多晶金属到半导体转变的密度泛函理论研究
二氧化钼(MoO2)由于其在催化、储能和电子器件方面的潜在应用而引起了人们越来越多的兴趣。已经预测了这种材料的几种理论上的多晶态,但它们的基本性质仍未被充分探索。在这项工作中,我们提出了一个全面的密度泛函理论(DFT)研究三种MoO2多晶(单斜晶(P21/c),四方晶(P42/mnm)和六边形晶(P63/mmc))的结构,磁性,电子和光学性质,特别强调顺磁性到反铁磁性和金属到半导体的转变。使用不同的交换相关泛函近似进行DFT计算。自旋极化计算表明,这三个相都是非磁性的。带结构分析表明,虽然单斜相和四方相仍然是金属相,但六方晶型的间接带隙为0.635 eV,表明Mo - 4d态的局部结构有序驱动了金属到半导体的转变。计算出的线性光学性质进一步支持了这些发现,证实了我们的理论方法的可靠性。总的来说,这些结果提供了有价值的见解,可以指导未来研究MoO2的相变及其对先进技术实际应用的潜在影响。
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来源期刊
Computational Condensed Matter
Computational Condensed Matter PHYSICS, CONDENSED MATTER-
CiteScore
3.70
自引率
9.50%
发文量
134
审稿时长
39 days
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