相对论赝势的从头计算法研究铀酰离子电子结构

Relativistic Pseudopotential ab initio Study of Electronic Structure in Uranyl Cations

用相对论赝势的从头算法研究了铀酰离子的几何构型和电子结构．得到了与实验数据较 一致的键长、健角和ＩＲ振动频率．铀氧间以 Ｕ５ｆ与 Ｏ２ｐ相互作用为主，Ｕ６ｄ与 Ｏ２ｐ间的健合较小； 同时， Ｕ６ｐ Ｕ７ｓ、 Ｕ６ｄ和 Ｕｓｄ杂化轨道与 Ｏ２ｓ间也有强的相互作用．不同自旋多重度时对铀酰离子总 能量计算结果表明，ＵＯ_２^(２＋)的基态为~1∑_g^+的可能性更大。

Geometry and electronic structure of uranyl cations have been calculated with harmonic vibration analysis, using relativistic effective core pseudopotential (RECP) method. The calculable bond lengthes and vibrational frequencies have compared favorably with experimental value. U5f-O2p bond dominates in the U-O bonding, while there are strong bonds between U6p, U6d, U7s and d-s hybridizing orbitals with O2s aloud orbital. The calculated results with dif- ferent spin multiplicity show that the ground state of UO_2^(2+) prefer ~1∑_g^+.