The electronic properties and defect chemistry of Gd-doped CeO₂ have been systematically investigated using the density functional theory with the Hubbard U correction. Three types of doping are considered in 2×2×2 CeO₂ supercell: one Gd substitution for Ce, one Gd substitution and one oxygen vacancy, and 2 Gd substitutions and an oxygen vacancy. Detailed thermodynamic and kinetic investigations have been conducted to elaborate the favorability for the formation of these dopants in CeO₂. Results show that Gd substitutions and oxygen vacancy tend to cluster in the form of Gd-V_O-Gd via strong interaction between donor (V_O) and acceptor (substitutional Gd) states. Such a donor-acceptor interaction is found to lead to charge compensation. In contrast, a single or isolated Gd substitution hardly influences the defect chemistry of oxygen vacancy. This work is expected to offer valuable insights into the Gd-doped CeO₂, beneficial for widening the practical applications of CeO₂-based materials and devices.

使用密度函数理论和Hubbard U校正系统地研究了掺Gd的CeO ₂的电子性质和缺陷化学。在2×2×2 CeO ₂超级电池中考虑了三种掺杂：一种是Ce的Gd替代，一种Gd替代和一种氧空位，以及2 Gd替代和一种氧空位。已经进行了详细的热力学和动力学研究，以阐明在CeO _2中形成这些掺杂剂的有利性。结果表明，钆置换和氧空位趋向于钆的形式簇V _ö施主之间经由强相互作用-Gd（V _Ò）和受体（替代Gd）状态。发现这种供体-受体相互作用导致电荷补偿。相反，单个或孤立的Gd取代几乎不会影响氧空位的缺陷化学。预期这项工作将为掺Gd的CeO ₂提供有价值的见解，有利于拓宽CeO ₂基材料和器件的实际应用。