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小型二氧化钛团簇(TiO_2)_n(n=2\sim8)的低能异构体研究

Low-Lying Isomers of (TiO_2)_n (n=2-8) Clusters

  • 摘要: 钛和氧之间存在多种成键方式,但迄今为止,二氧化钛团簇均只有少数几种异构体被报道. 与广泛使用的全局优化方法不同,本工作通过优化大量的随机初始结构,获得(TiO_2)_n(n=2\sim8)团簇稳定异构体. 首先利用PM6半经验方法对高达一万个以上的初始结构进行初步的优化筛选,并对筛选出的结构进行进一步的DFT计算以获得二氧化钛团簇的稳定异构体. 利用这种策略,发现了大量未经报道的稳定异构体,并提出了(TiO_2)_5和(TiO_2)_8新的最稳定异构体. 这些结构中包括含3个末端氧原子的异构体、含5配位氧原子和6配位钛原子的异构体等未经报道的新结构类型. 与丰富成键特征相对应,发现异构体数目随团簇尺寸的增大而急剧增加,对于(TiO_2)_7和(TiO_2)_8,能量在30 kcal/mol以内的异构体都在50个以上. 该工作发现了大量的二氧化钛小型团簇异构体,并凸显了其多样的结构特征,增进了对二氧化钛纳米团簇的结构、成键的理解,并为进一步的理论模拟、力场优化等提供了理论基础.

     

    Abstract: Although there are diverse bond features of Ti and O atoms, so far only several isomers have been reported for each (TiO_2)_n cluster. Instead of the widely used global optimization, in this work, we search for the low-lying isomers of (TiO_2)_n (n=2-8) clusters with up to 10000 random sampling initial structures. These structures were optimized by the PM6 method, followed by density functional theory calculations. With this strategy, we have located many more low-lying isomers than those reported previously. The number of isomers increases dramatically with the size of the cluster, and about 50 isomers were found for (TiO_2)_7 and (TiO_2)_8 with the energy within kcal/mol. Furthermore, new lowest isomers have been located for (TiO_2)_5 and (TiO_2)_8, and isomers with three terminal oxygen atoms, five coordinated oxygen atoms as well as six coordinated titanium atoms have been located. Our work highlights the diverse structural features and a large number of isomers of small TiO_2 clusters.

     

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