PNNL

Abstract

A first-principles method has been employed to investigate the structural and energetic properties for A2Ti2O7 (A=Lu, Er, Y, Gd, Sm, Nd, La), including the formation energies of the cation antisite-pair, the anion Frenkel pair that defines anion-disorder, and the coupled cation antisite-pair/anion-Frenkel. It is proposed that the interaction may have more significant influence on the radiation resistance behavior of titanate pyrochlores, although the interactions are relatively much stronger than the interactions. It is found that the defect formation energies are not simple functions of the A-site cation radii. The formation energy of the cation antisite-pair increases continuously as the A-site cation varies from Lu to Gd, and then decreases continuously with the variation of the A-site cation from Gd to La, in excellent agreement with the radiation-resistance trend of the titanate pyrochlores. The band gaps in these pyrochlores were also measured, and the band gap widths changed continuously with cation radius.