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针对电子极化子迁移的哈伯德U修正受限密度泛函理论方法:TiO2实例研究

Constrained Density Functional Theory Plus the Hubbard U Correction Approach for the Electronic Polaron Mobility: A Case Study of TiO2

  • 摘要: 极化子的形成和迁移对过渡金属氧化物的物理和化学性质有重要影响. 含哈伯德U修正的密度泛函理论和受限密度泛函理论方法经常被应用于小极化子迁移性质的理论研究. 本文在投影缀加波框架中实现了哈伯德U修正的受限密度泛函理论(cDFT+U),并将其应用于体相TiO_2中的极化子迁移性质的计算. 确认了哈伯德U的取值对极化子性质的理论预测有重要影响. 采用基于cDFT计算所获得的哈伯德U值,可对TiO_2金红石和锐钛矿相中的极化子性质获得与实验符合很好的描述. 本文表明,使用与理论上一致的方式计算获得的哈伯德U值,cDFT+U有望成为一种有效的不需经验输入而计算过渡金属氧化物极化子性质的第一性原理方法.

     

    Abstract: The formation and migration of polarons have important influences on physical and chemical properties of transition metal oxides. Density functional theory plus the Hubbard U correction (DFT+U) and constrained density functional theory (cDFT) are often used to obtain the transfer properties for small polarons. In this work we have implemented the cDFT plus the Hubbard U correction method in the projector augmented wave (PAW) framework, and applied it to study polaron transfer in the bulk phases of TiO_2. We have confirmed that the parameter U can have significant impact on theoretical prediction of polaronic properties. It was found that using the Hubbard U calculated by the cDFT method with the same orbital projection as used in DFT+U, one can obtain theoretical prediction of polaronic properties of rutile and anatase phases of TiO_2 in good agreement with experiment. This work indicates that the cDFT+U method with consistently evaluated U is a promising first-principles approach to polaronic properties of transition metal oxides without empirical input.

     

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