醋酸铀酰负离子气相分解反应的密度泛函理论研究  

Density Functiond Theory Study on Decomposition Reaction of Organic Uranyl Acetate in Gas Phase

作　　者：于立安[1] 胡斌[1] 罗明标[1] 张燮[1] 陈焕文[1] 

机构地区：[1]东华理工大学应用化学系,抚州344000

出　　处：《高等学校化学学报》2009年第12期2460-2463,共4页Chemical Journal of Chinese Universities

基　　金：国防基础科研基金项目(批准号:A3420060146);东华理工大学研究生创新基金(批准号:DYCA09001)资助

摘　　要：采用密度泛函理论(DFT),选择杂化密度泛函TPSSh和TZVP基组,对一个UO2(CO3)43-负离子的结构进行优化,理论计算所得结果(键长等参数)与实验数据一致.应用TPSSh/TZVP(ECP)方法对醋酸铀酰负离子UO2(CH3COO)3-的气相分解反应进行了理论计算,成功地解释了含+5价铀的气相自由基负离子的稳定性,并对2个负离子(CH3COO)UO2CH3-和CH3UO2OH-分别与水的复分解反应进行了理论计算,所得数据与质谱的实验结果较好地吻合.A quantum chemical model was established for theoretical studies by employing the widely used density functional theory（DFT）, the selected hybrid functional TPSSh in combination with TZVP basis set and an effective core potential（ECP） for uranium atom. As a test calculation, the structure of a complex UO2（CO3）34- was optimized with the above-mentioned TPSSh/TZVP（ECP） method, it was found that the calculated results（bond distances） are in good agreement with the experimental data. Then, we investigated the decomposition reaction of the anion UO2（CH3COO）3- with this method. The results indicate that the uranyl（＋5） radical specie is the most stable state in the gas phase. The two decomposition reactions of the species（CH3COO）UO2CH3- and CH3UO2OH- with water were also simulated with the above-mentioned method and the obtained results agree well with the mass spectroscopy data.

关 键 词：密度泛函理论 TPSSh 醋酸铀酰 自由基 分子离子反应 

分 类 号：O641[理学—物理化学]