化学学报 ›› 2000, Vol. 58 ›› Issue (11): 1345-1348. 上一篇    下一篇

研究论文

HX体系电子对内、对间相关研究

殷平;陈先阳;姚天扬;居冠之;李重德;忻新泉   

  1. 南京大学化学系.南京(210008);南京大学配位化学国家重点实验室.南京 (210008);上海交通大学应用化学系.上海(200030)
  • 出版日期:2000-11-15 发布日期:2000-11-15

Studies on the intrapair and interpair correlation of electrons of HX

Yin Ping;Chen Xianyang;Yao Tianyang;Ju Guanzhi;Li Zhongde;Xin Xinquan   

  1. Nanjing Univ, Dept Chem.Nanjing(210008);Nanjing Univ, Coordinat Chem State Key Lab.Nanjing(210008);Shanghai Jiao Tong Univ, Dept Appl Chem. Shanghai(200030)
  • Online:2000-11-15 Published:2000-11-15

在6-311+G^*基组水平上用CISD(configurationinteractionwithsinglyanddoublyexcitedconfigurations)方法研究HX(X=Li-F,HBe)体系电子对内、对间的相关能。计算结果表明不同元素形成的HX(X=Li-F,HBe^+,HBe)体系,其价层电子对内、对间相关能的变化较大,它们之间存在着轨道差别,不宜将其相关贡献归为简单的常数。在使用相同理论方法和相同质量基组的前提下,电子数将直接影响到电子对间相关能的大小。对于多电子体系,电子对间相关在总相关中占有优势,若将其忽略会引起较大误差。

关键词: 氢化锂, 氟化氢, 氢化铍, 电子对内相关, 电子对间相关

The intrapair and interpair correlation energies of electrons of HX (X=Li-F, HBe^+, HBe) have been studied by CISD(configuration interaction with singly and doubly excited configuration)method with 6-311+G^* basis set. It has been found that the electron intrapair and interpair correlation energies are very sensible to orbitals (except the inner orbitals). furthermore, the changes of intrapair and interpair energies of valence electrons are very great in the different element-formed systems. Under the conditions of the same theoretical method and the same basis sets, the number of electrons will affect directly the vlues of interpair correlation energies of electrons. If a system has many electrons, the total electron interpair correlation energy will dominate in the total electron correlation energy. this remine\ds us that we should take the importance of interpair of electrons and the difference of orbitals into consideration while further correcting the caculated result of Post-HF.

Key words: LITHIUM HYDRIDE, HYDROGEN FLUORIDE

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