Ben Yahia Mouna, Lemoigno Frédéric, Beuvier Thomas, Filhol Jean-Sébastien, Richard-Plouet Mireille, Brohan Luc, Doublet Marie-Liesse
Institut Charles Gerhardt Montpellier UMR 5253 CNRS-UM2-ENSCM-UM1 Université Montpellier 2, 34095 Montpellier, France.
J Chem Phys. 2009 May 28;130(20):204501. doi: 10.1063/1.3130674.
To get updated references on the structural, electronic, and vibration properties of the metastable TiO(2)(B) compound, infrared and Raman spectra of TiO(2)(B) are computed within the density functional theory framework and all active modes are assigned. Phonons and their possible coupling with the macroscopic electric fields resulting from the long-range interactions of instantaneous local dipoles (due to nuclear vibrations) in polar solids are taken into account through supercell calculations and longitudinal optical-transversal optical splitting corrections. Full structural relaxations using conventional density functional theory and hybrid functionals with localized Gaussian-type orbitals or plane-wave basis sets reveal a similar deviation of the local Ti environment compared to the TiO(2)(B) structural refinements reported so far. Such deviations are shown to be significant from those computed for anatase using the same method, thus yielding distinguishable spectroscopic responses for the two polymorphs.
为获取关于亚稳TiO₂(B)化合物的结构、电子和振动性质的最新参考文献，在密度泛函理论框架内计算了TiO₂(B)的红外光谱和拉曼光谱，并对所有活性模式进行了归属。通过超胞计算和纵向光学-横向光学分裂校正，考虑了声子及其与极性固体中瞬时局部偶极子（由于核振动）的长程相互作用所产生的宏观电场的可能耦合。使用传统密度泛函理论以及带有定域高斯型轨道或平面波基组的杂化泛函进行的完全结构弛豫显示，与迄今报道的TiO₂(B)结构精修相比，局部Ti环境存在类似偏差。结果表明，这些偏差与使用相同方法为锐钛矿计算的偏差显著不同，从而使两种多晶型具有可区分的光谱响应。
