Materials Chemistry, The Angström Laboratory, Uppsala University, Box 538, S-751 21 Uppsala, Sweden.
J Chem Phys. 2010 Feb 7;132(5):054110. doi: 10.1063/1.3253795.
In this paper we evaluate the performance of density functional theory with the B3LYP functional for calculations on ceria (CeO(2)) and cerium sesquioxide (Ce(2)O(3)). We demonstrate that B3LYP is able to describe CeO(2) and Ce(2)O(3) reasonably well. When compared to other functionals, B3LYP performs slightly better than the hybrid functional PBE0 for the electronic properties but slightly worse for the structural properties, although neither performs as well as LDA+U(U=6 eV) or PBE+U(U=5 eV). We also make an extensive comparison of atomic basis sets suitable for periodic calculations of these cerium oxides. Here we conclude that there is currently only one type of cerium basis set available in the literature that is able to give a reasonable description of the electronic structure of both CeO(2) and Ce(2)O(3). These basis sets are based on a 28 electron effective core potential (ECP) and 30 electrons are attributed to the valence space of cerium. Basis sets based on 46 electron ECPs fail for these materials.
在本文中，我们评估了密度泛函理论中 B3LYP 函数在氧化铈（CeO(2)）和三氧化二铈（Ce(2)O(3)）计算中的性能。我们证明 B3LYP 能够很好地描述 CeO(2)和 Ce(2)O(3)。与其他泛函相比，B3LYP 在电子性质方面的表现略优于混合泛函 PBE0，但在结构性质方面的表现略差，尽管这两种泛函都不如 LDA+U（U=6 eV）或 PBE+U（U=5 eV）好。我们还对这些铈氧化物的周期性计算适用的原子基组进行了广泛的比较。在这里，我们得出结论，目前文献中只有一种类型的铈基组能够合理地描述 CeO(2)和 Ce(2)O(3)的电子结构。这些基组基于 28 电子有效核势（ECP），其中 30 个电子归属于铈的价电子空间。对于这些材料，基于 46 个电子 ECP 的基组会失效。
