物理化学学报 >> 2002, Vol. 18 >> Issue (02): 117-121.doi: 10.3866/PKU.WHXB20020205

研究论文 上一篇    下一篇

NX(X=F,Cl,Br)分子结构与极化函数f轨道的作用

刘幼成;蒋刚;朱正和   

  1. 四川大学原子与分子物理所,成都 610065
  • 收稿日期:2001-07-19 修回日期:2001-10-04 发布日期:2002-02-15
  • 通讯作者: 蒋刚 E-mail:gjiang@pridns.scu.edu.cn

Molecular Structure for NX(X=F,Cl,Br) and the Contribution of Polarization Functions f Orbitals

Liu You-Cheng;Jiang Gang;Zhu Zheng-He   

  1. Institute of Atomic and Molecular Physics,Sichuan University,Chengdu 610065
  • Received:2001-07-19 Revised:2001-10-04 Published:2002-02-15
  • Contact: Jiang Gang E-mail:gjiang@pridns.scu.edu.cn

摘要: 用密度泛函理论的Becke3LYP方法,计算了NX(X=F,Cl,Br)的激发态b1Σ+ 和基态X3Σ-,并对比不含f轨道的基集合cc-pvDZ和6-311+G与含f轨道的基集合6-311+G(3df)的计算结果,发现极化函数f轨道对NCl和NBr的键长与谐振频率ωe有明显改进作用,即f轨道对成键有贡献,而f轨道对NF的Re和ωe则无明显作用.同时,基于能量共振转移的需要,用NF代替O2-I 红外激光系统的O2是不适宜的,而用NCl和NBr代替则是可能的.

关键词: NX(X=F,Cl,Br)分子, 密度泛函理论, f轨道极化函数

Abstract: Excited states b1Σ+ and ground states X3Σ- for molecules NX(X=F,Cl,Br) have been calculated using density functional theory(DFT) Becke 3LYP.In comparison of the calculated results with f orbitals basis set 6-311+G(3df) and that without f orbitals basis sets cc-pvDZ and 6-311+G,it is instructive to notice that the polarization function f orbitals significantly contribute to improve in bond lengths Re and vibration frequencies ωe for NCl and NBr,but not for NF.Therefore,the f orbitals not only play some subtle aspects in bonding for lanthanides and actinides,but also for the elements lighter than lanthanum.

Key words: NX(X=F,Cl,Br) molecules, Density functional theory, Polarization function f orbitals