Al(H_2O)^(3+)_6水交换反应溶剂效应的量子化学团簇模型-密度泛函理论方法研究  

Investigation of the Solvent Effects for the Water-Exchange Reactions of Al( H_2O)^(3+)_6 by Quantum Chemical Cluster Models-Density Functional Theory Method

作　　者：张婧[1] 董绍楠 侯晓霞[1] 袁晓涵 毕树平[1] 

机构地区：[1]南京大学化学化工学院,江苏南京210023

出　　处：《分析科学学报》2017年第5期649-654,共6页Journal of Analytical Science

基　　金：国家自然科学基金(No.21177054)

摘　　要：在气相模型、极化连续模型、超分子模型和超分子-极化连续模型的基础上,采用量子化学团簇模型-密度泛函理论方法,在B3LYP/6-311+G(d,p)基组水平下系统地开展了以下研究:优化得到Al(H_2O)^(3+)_6水交换反应的反应物、过渡态和产物构型,采用MP2方法在相同基组水平下计算得到相应的单点能,考虑零点振动能、热力学校正项和熵等参数的影响,计算得到Al(H_2O)^(3+)_6水交换反应的Gibbs自由能变和反应速率常数k_(ex)。计算结果表明:GP-SM//MP2-PCM和GP-SM-PCM//MP2-PCM模型得到的k_(ex)相近,并且与文献值相符,说明GP-SM//MP2-PCM模型可以充分考虑真实溶剂效应和主体溶剂效应,适用于Al(H_2O)^(3+)_6体系水交换反应的模拟。Based on the four models （gas phase （GP）, polarizable continuum model （GP-PCM）, supermolecule model（GP-SM） and supermolecule-polarizable continuum model （ GP-SM-PCM））, we systematically conducted the following investigations using quantum chemical cluster models-density functional theory method. The water-exchange reaction of AI（H2O）3＋6 was simulated at the level of B3LYP/6-311＋G（d, p） ,and the single-point energies were calculated using MP2 method. Taking zero-point energies, thermal corrections and entropies into consideration, the activation Gibbs energy barries and water-exchange rate constant（kex） were calculated. The logkex values for water-exchange reactions of AI（H2 O）3＋6 with GP- SM//MP2-PCM and GP-SM-PCM//MP2-PCM models were similar and consistent with available literature values. This indicates that the GP-SM//MP2-PCM model could simulate the water-exchange reaction of AI（H2 O）3＋6satisfactorily.

关 键 词：Al(H2O)3+6 水交换反应 量子化学团簇模型 密度泛函理论 溶剂效应 

分 类 号：P65[天文地球—地质学]