【作者】 李权；

【导师】 朱正和；

【作者基本信息】 四川大学 ， 原子分子物理， 2001， 博士

【摘要】 用原子分子反应静力学（AMRS）原理研究得到PuOⁿ⁺，PuHⁿ⁺，PuNⁿ⁺和PuCⁿ⁺分子离子的电子状态及其离解极限。在Pu的相对论有效原子实势（RECP）近似下，用量子力学密度泛函理论（DFT）方法B3LYP研究表明，正三价分子离子PuO³⁺，PuH³⁺，PuN³⁺，PuC³⁺不能稳定存在。正一价分子离子PuO⁺，PuH⁺，PuN⁺，PuC⁺和正二价分子离子PuO²⁺，PuH²⁺，PuN²⁺，PuC²⁺能稳定存在，势能函数为Murrell-Sorbie函数，并导出了相应的光谱数据和力学性质。通过对双原子分子离子稳定存在与否的分析讨论提出双原子分子离子的稳定性与其离解通道相关。 用AMRS原理导出基态PuCO分子和基态PuH₂分子的电子状态及其离解极限。结构优化表明，PuCO基态分子的稳定构型为角形C_s结构，基态电子状态为X⁷A″。PuH₂基态分子的稳定构型为角形C_2v结构，基态电子状态为X⁷A₁。用多体项展式理论方法拟合得到基态PuCO分子和基态PuH₂分子的解析势能函数，并绘出了相应的等值势能图，分析了势能面上碰撞反应的静态特征。 基于PuCO基态分子的解析势能函数，用准经典的Monte-Carlo轨迹法研究Pu+CO和O+PuC的碰撞反应动力学过程。结果表明，Pu+CO碰撞反应易生成PuCO络合物分子，该反应是无阈能反应，反应截面随能量E_t的增加而降低。O+PuC碰撞反应容易生成CO+Pu的交换反应，该反应是无阈能反应，反应截面随E_t的增加而降低。更多还原

【Abstract】 Potential energy function and stability for PuOn+PuH^PuN" + and PuCn+(n= 1,2,3) molecular ions, potential energy function and the rmodynamic stability for PuCO and PuH2 ground state molecules, and quasi-class ical molecular reactive dynamical processes have been studied in present research .Firstly, using the Atomic and Molecular Reactive Statics (AMRS), the electronic states and the corresponding reasonable dissociative limits for PuOn+,PuHn+,PuNn+ and PuCn+ molecular ions have been derived Considering the Relativistic Effective Core Potential(RECP) for atom Pu and all-electron basis 6-311G* for the other elements, the theoretical study on PuOn+,PuH"+,PuNn + and PuCn+ molecular ions using Densit y Functional Theory (DFT) B3LYP shows that PuO3+ ,PuH3+,PuN3+ and PuC3+ can not be stable.PuO+,PuH+,PuN+, PuC+ and PuO2+,PuH2+,PuN2+,PuC2+ can be stable, and their potential energy functions are in well argreemeet with the Murrell-Sorbie function, and their force constants and spectroscopic data have been worked out.And then the ground electronic states and the reasonable dissociative limits of PuCO and PuH2 molecules are also derived based on the AMRS. The optimized results show that the ground electronic states are 7A" for PuCO molecules and 7A, for PuH2 molecules. The analytical potential energy functions for PuCO and PuH2 have been fitted out using the many-body expansion method.The atomic and molecular reaction dynamic processing for the collision Pu+CO and O+PuC have been studied based on the present potential energy function of PuCO by the Monte-Carlo quasi-classical trajectory approach. The results indicate that complexes PuCO molecules are easily formed, the collisional complexes reaction Pu +CO- PuCO have no threshold energy, and the reaction cross section will decrease as the increase of Et, and O+PuC- Pu+CO have no threshold energy , and the reaction cross section will decrease as the increase of Et.更多还原