水交換反應溶劑效應的量子化學團簇模型-密度泛函理論方法研究

張 婧， 董紹楠， 侯曉霞， 袁曉涵， 畢樹平

(南京大學化學化工學院，江蘇南京 210023)

1 計算方法

表1 不同優(yōu)化模型與單點能計算方法下的能量表達方式

2 結果與討論

圖1 四大模型下水交換反應的反應物、過渡態(tài)以及產物的構型圖(離去水以白色標記)Fig.1 The reactants,transition states and products for water-exchange reactions of complex with four models(the leaving water molecules are colored white to differ from others)

表2 四大模型下水交換反應的反應物、過渡態(tài)和產物的結構參數(shù)

Note:athe distances between Al and O of coordinated H2O;bthe average bond length between Al and O of coordinated H2O;cthe distance between Al and O of leaving H2O;dthe sum of Al-O bond lengths;eΔΣr(Al-O)I=Σr(Al-O)I,transition state-Σr(Al-O)I,reactant.

表3 四大模型下水交換反應的反應物、過渡態(tài)和產物的氫鍵鍵長(?)

圖2 不同溶劑效應下水交換反應的Gibbs自由能變化(A)和反應速率常數(shù)對數(shù)logkex(B)(圖中(A)和(B)的1-8分別對應表1中的8組能量)Fig.2 The Gibbs free energy changes (A) and logkex (B) for the water-exchange reactions of with different solvent effects(1-8 in(A) and(B) are corresponding to the energies in the Table 1)

3 結論