二价金属离子对含铜水滑石结构稳定性的影响.pdfVIP

[Article] 物理化学学报(Wuli Huaxue Xuebao) Acta Phys. -Chim. Sin. 2012, 28 (7), 1707-1713July Received: March 15, 2012; Revised: May 11, 2012; Published on Web: May 11, 2012. ∗Corresponding author. Email: wangf@; Tel: +86-28 The project was supported by the National Natural Science Foundation of China . 国家自然科学基金资助项目 Ⓒ Editorial office of Acta Physico-Chimica Sinica doi: 10.3866/PKU.WHXB201205111 等电子三原子铀化物OUO2+、NUN和NUO+的结构和谐振频率的 CCSD(T)计算研究 涂喆研 1 杨冬冬 1 王 繁 1,* 李象远 2 (1四川大学化学学院,成都 610064; 2四川大学化工学院,成都 610065) 摘要: 用小核相对论有效势和CCSD(T)方法计算了三原子铀化物OUO2+, NUN和NUO+的平衡键长和谐振频 率.计算结果显示U原子内层5s5p5d电子相关能对这些化合物性质的影响非常小.除NUN的弯曲振动频率, 旋轨耦合效应对这些化合物的结构和频率的影响并不明显.本文的计算结果与其他研究组的计算结果以及已有 的实验值相比符合较好,这表明作为单参考态方法, CCSD(T)能够对这些体系的键长和频率给出较精确的计算 结果.与此前密度泛函理论(DFT)的计算结果相比, CCSD(T)方法与PBE0泛函的结果吻合最好.本文的工作有 助于在用密度泛函方法研究这些体系时选择合适的交换相关泛函,也为今后的实验研究提供了新的理论数据. 关键词: 铀化物; 耦合簇理论; 旋轨耦合 中图分类号: O641 A CCSD(T) Study on Structures and Harmonic Frequencies of the Isoelectronic Uranium Triatomic Species OUO2+, NUN and NUO+ TU Zhe-Yan1 YANG Dong-Dong1 WANG Fan1,* LI Xiang-Yuan2 (1College of Chemistry, Sichuan University, Chengdu 610064, P. R. China; 2College of Chemical Engineering, Sichuan University, Chengdu 610065, P. R. China) Abstract: CCSD(T) calculations with small-core relativistic effective core potentials for equilibrium bond lengths and harmonic frequencies are presented for uranium triatomic OUO2 + , NUN, and NUO + species. The inner shell electron correlation of the U atom has almost no effect on the properties of these species, and the spin-orbit coupling only has a small effect, except in the bending mode of NUN. Our results agree reasonably well with previous theoretical results and the available experimental data, which indicates that the single-reference CCSD(T) method can be employed to study these species. Compared with previous results, the CCSD(T) results agree best with density functional theory (DFT) calculations performed using the PBE0 functional. The present work prov