PuO_3和PuO_3^+的分子结构与分子光谱  

Molecular Structures and Molecular Spectra for PuO_3 and PuO_3^+

作　　者：高涛[1] 朱正和[1] 汪小琳[2] 孙颖[2] 蒙大桥[2] 

机构地区：[1]四川大学(西区)原子与分子物理研究所,成都610065 [2]中国工程物理研究院,绵阳621900

出　　处：《化学学报》2004年第5期454-460,共7页Acta Chimica Sinica

基　　金：国家自然科学基金 (No.1 0 1 760 1 7);中国工程物理研究院基金 (No.2 0 0 0z0 50 3)资助项目

摘　　要：用相对论有效原子实势RECP和密度泛函 (B3LYP ,BHANDHLYP)、HF方法对PuO3 的分子结构与分子光谱进行了研究 .计算比较了C2v,D3h,C3v等构型以及计算方法等对PuO3 分子能量和平衡结构的影响 ,结果表明中性的PuO3 能够稳定存在 ,基态结构为C2v,状态为7B1(B3LYP :R1=0 .1914 3nm ,R2 ( =R3 ) =0 .2 2 0 5 7nm ,∠OPuO =10 2 .2 10 8°) ,比较而言PuO3分子还可能存在D3h结构的亚稳态7A2 ″ ,不存在稳定的C3v结构的PuO3 分子 .计算还同时首次给出了不同多重性的PuO3 分子及其一价正离子PuO+ 3 完整的能量、平衡几何结构、光谱数据、电荷布居、自旋密度。The molecular structures and spectra for PuO_3 are worked out by ab initio HF, and density functional B3LYP and BHANDHLYP methods with relativistic effective core potential (RECP) for Pu atom and 6-31+g * for O atom. The effects of symmetry C_ 2v, D_ 3h and C_ 3v for the four atoms PuO_3 molecule, the calculation levels on molecular energies, and equilibrium structures have been evaluated. The results show that the neutral PuO_3 molecule could exist stably in C_ 2v structure (B3LYP: R_1=0.19143 nm, R_2(=R_3)=0.22057 nm, ∠OPuO=102.2108°), its ground electronic state is 7B_1, the D_ 3h structure could be assigned to a metastable state 7A_2″, and there would be no stable C_ 3v structure. The corresponding vibrational harmonic frequencies, vibrational infrared intensities, Raman activities, Raman depolarizabilities, Mulliken charge populations, spin densities, polarizabilities and electric dipole moments have also been tabled out at first time. The same calculations performed on PuO +_3 ion also show that the C_ 2v structure could exist stably, and its ground state is 6B_2.

关 键 词：氧化钚 钚酸根离子 分子结构 分子光谱 密度泛函 相对论有效原子实势 

分 类 号：O641[理学—物理化学]