DFT study on O₂ adsorption on a nanocrystalline titania is presented for the first time. The dioxide’s nanoparticle is modeled via the nanocluster Ti₈O₁₆. According to the calculations, O₂ physisorbs on the nanocluster Ti₈O₁₆ in S⁰ and T⁰ states and chemisorbs on the nanocluster in S¹ state. The computed adsorption enthalpies, O₂ vibrational frequencies, and O₂^-g-tensor agree well with available data. In contrast to the axial O₂ orientation on a surface of titania with oxygen vacancies, in the chemisorption complex O₂ is oriented laterally. We explain this by the sterical hindrance of the Ti³⁺ centers in the former case.

首次提出了在纳米晶二氧化钛上吸附O _2的DFT研究。二氧化钛的纳米粒子是通过纳米团簇Ti ₈ O ₁₆建模的。根据计算，O ₂在S ⁰和T ⁰状态的纳米团簇Ti ₈ O ₁₆上发生物理吸附，而在S ¹状态的纳米团簇上发生化学吸附。计算得到的吸附焓，O ₂振动频率和O ₂ ^- g-张量与可用数据非常吻合。与轴向O ₂相反化学吸附复合物中的O ₂在具有氧空位的二氧化钛表面上取向为横向​​。我们通过前者中Ti ³⁺中心的空间位阻来解释这一点。