论文部分内容阅读
采用密度泛函理论研究了Keggin型α-[HxW12O40](8–x)–(x=1~4)的中心容纳质子数以及中心质子通过Keggin笼腔进行内外转移的机理.在O3LYP/LanL2DZ水平下,对气相中各物种结构进行了全优化,得到了质子化前后各物种的稳定构型,找到了质子通过笼腔进行内外转移的过渡态,并用频率分析方法和内禀反应坐标(IRC)方法对各过渡态进行了确证.在极化连续介质模型(PCM)下,考察了体系的溶剂化效应.理论研究不仅阐述了颇有争议的单质子中心和4质子中心物种存在的可能性,而且揭示了质子通过Keggin金属氧笼进行转移和传递的微观机制,理论计算结果与实验事实相一致.
Density functional theory (DFT) was used to study the mechanism of the central proton number of Kegginα- [HxW12O40] (8-x) - (x = 1-4) and the central and proton proton transfer inside and outside through Keggin cage.At the O3LYP / LanL2DZ level , The structure of each species in the gas phase was fully optimized, the stable configuration of each species before and after protonation was obtained, and the transition state of proton transfer inside and outside was found through the cage cavity. The frequency analysis method and intrinsic reaction coordinate (IRC) Method was used to confirm each transition state.The solvation effect of the system was investigated under a polarized continuum model.The theoretical study not only described the possibility of the existence of the controversial single proton centers and 4 proton center species, But also reveals the microscopic mechanism of proton transfer and transfer through Keggin metal oxygen cage. The theoretical calculation results are consistent with experimental facts.