Zhang Yong-fan, Lin Wei, Li Yi, Ding Kai-ning, Li Jun-qian
Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350002, China.
J Phys Chem B. 2005 Oct 20;109(41):19270-7. doi: 10.1021/jp0523625.
The effects of the Fock exchange on the geometries and electronic structures of TiO2 have been investigated by introducing a portion of Hartree-Fock (HF) exchange into the traditional density functional. Our results indicate that the functional with 13% HF exchange can correctly predict the band gap and the electronic structures of rutile TiO2, and such an approach is also suitable to describe the structural and electronic properties of anatase and brookite phases. For the TiO2 (110) surfaces, although the surface relaxations are insensitive to the variation of HF exchange, there are larger effects on the positions of the occupied surface-induced states. When 13% HF exchange is employed, the predicted band gap of the perfect surface and position of defect state of the reduced surface are consistent with the experimental values. Moreover, the electronic structures of TiO2 (110) surface are carefully reexamined by using this hybrid density functional method.
通过将一部分哈特里-福克（HF）交换引入传统密度泛函，研究了福克交换对TiO₂几何结构和电子结构的影响。我们的结果表明，具有13%HF交换的泛函能够正确预测金红石型TiO₂的带隙和电子结构，并且这种方法也适用于描述锐钛矿型和板钛矿型相的结构和电子性质。对于TiO₂（110）表面，虽然表面弛豫对HF交换的变化不敏感，但对占据的表面诱导态的位置有较大影响。当采用13%HF交换时，完美表面的预测带隙和还原表面的缺陷态位置与实验值一致。此外，利用这种杂化密度泛函方法对TiO₂（110）表面的电子结构进行了仔细的重新研究。
