CAJ | 학술논문

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UO_2(CO_3)_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UO_2(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(CH_3 COO)UO_2 CH_3~-和CH_3UO_2PH~-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.
채용밀도범함이론(DFT),선택잡화밀도범함TPSSh화TZVP기조,대일개UO_2(CO_3)_3~(4-)부리자적결구진행우화,이론계산소득결과(건장등삼수)여실험수거일치.응용TPSSh/TZVP(ECP)방법대작산유선부리자UO_2(CH3COO)_3~-적기상분해반응진행료이론계산,성공지해석료함+5개유적기상자유기부리자적은정성,병대2개부리자(CH_3 COO)UO_2 CH_3~-화CH_3UO_2PH~-분별여수적복분해반응진행료이론계산,소득수거여질보적실험결과교호지문합.
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 UO_2 (CO_3 )_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 UO_2 (CH_3 COO )_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(CH_3 COO)UO_2CH_3~- and CH_3 UO_2OH~- with water were also simulated with the above-mentioned method and the obtained results agree well with the mass spectroscopy data.