醋酸铀酰负离子气相分解反应的密度泛函理论研究

高等学校化学学报 ›› 2009, Vol. 30 ›› Issue (12): 2460.

醋酸铀酰负离子气相分解反应的密度泛函理论研究

于立安, 胡斌, 罗明标, 张燮, 陈焕文

东华理工大学应用化学系, 抚州 344000

收稿日期:2009-01-30 出版日期:2009-12-10 发布日期:2009-12-10
通讯作者: 罗明标, 男, 博士, 教授, 主要从事放射性元素分析化学研究. E-mail: mbluo@126.com
基金资助:
国防基础科研基金项目(批准号: A3420060146)和东华理工大学研究生创新基金(批准号: DYCA09001)资助.

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

YU Li-An, HU Bin, LUO Ming-Biao*, ZHANG Xie, CHEN Huan-Wen

Applied Chemistry Department, East China Institute of Technology, Fuzhou 344000, China

Received:2009-01-30 Online:2009-12-10 Published:2009-12-10
Contact: LUO Ming-Biao. E-mail: mbluo@126.com
Supported by:
国防基础科研基金项目(批准号: A3420060146)和东华理工大学研究生创新基金(批准号: DYCA09001)资助.

摘要/Abstract

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)₃^4-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.

关键词: 密度泛函理论; TPSSh; 醋酸铀酰; 自由基; 分子离子反应

Abstract:

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)₃^4- 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.

Key words: Density functional theory; TPSSh; Uranyl acetate; Radical; Ion/molecule reaction

TrendMD:

于立安, 胡斌, 罗明标, 张燮, 陈焕文. 醋酸铀酰负离子气相分解反应的密度泛函理论研究. 高等学校化学学报, 2009, 30(12): 2460.

YU Li-An, HU Bin, LUO Ming-Biao*, ZHANG Xie, CHEN Huan-Wen. Density Functiond Theory Study on Decomposition Reaction of Organic Uranyl Acetate in Gas Phase. Chem. J. Chinese Universities, 2009, 30(12): 2460.

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