Beijing Computational Science Research Center, Beijing 100084, People's Republic of China.
Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599, USA.
J Chem Phys. 2017 Oct 7;147(13):134303. doi: 10.1063/1.5004406.
Condensed-to-atom Fukui functions which reflect the atomic reactivity like the tendency susceptible to either nucleophilic or electrophilic attack demonstrate the bonding trend of an atom in a molecule. Accordingly, Fukui functions based concepts, that is, bonding reactivity descriptors which reveal the bonding properties of molecules in the reaction were put forward and then applied to pericyclic and cluster reactions to confirm their effectiveness and reliability. In terms of the results from the bonding descriptors, a covalent bond can readily be predicted between two atoms with large Fukui functions (i.e., one governs nucleophilic attack while the other one governs electrophilic attack, or both of them govern radical attacks) for pericyclic reactions. For SiO clusters' reactions, the clusters with a low O atom ratio readily form a bond between two Si atoms with big values of their Fukui functions in which they respectively govern nucleophilic and electrophilic attacks or both govern radical attacks. Also, our results from bonding descriptors show that Si-Si bonds can be formed via the radical mechanism between two Si atoms, and formations of Si-O and O-O bonds are possible when the O content is high. These results conform with experimental findings and can help experimentalists design appropriate clusters to synthesize Si nanowires with high yields. The approach established in this work could be generalized and applied to study reactivity properties for other systems.
缩合到原子的 Fukui 函数反映了原子的反应性，类似于亲核或亲电攻击的倾向，展示了分子中原子的成键趋势。因此，提出了基于 Fukui 函数的概念，即揭示分子在反应中键合性质的键反应描述符，并将其应用于周环和团簇反应，以确认其有效性和可靠性。根据键描述符的结果，对于周环反应，可以预测两个 Fukui 函数较大的原子（即一个控制亲核攻击，另一个控制亲电攻击，或者两者都控制自由基攻击）之间容易形成共价键。对于 SiO 团簇的反应，O 原子比例低的团簇容易在 Fukui 函数较大的两个 Si 原子之间形成键，其中它们分别控制亲核和亲电攻击或两者都控制自由基攻击。此外，我们的键描述符结果表明，两个 Si 原子之间可以通过自由基机制形成 Si-Si 键，并且当 O 含量高时，Si-O 和 O-O 键的形成是可能的。这些结果与实验结果一致，可以帮助实验人员设计合适的团簇，以高产率合成硅纳米线。这项工作中建立的方法可以推广并应用于研究其他体系的反应性性质。
