摘要
在6-311+G~*基组水平上用CISD(configuration interaction with singly and doubly excited configurations)方法研究HX(X=Li-F,HBe^+,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.
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 configurations)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 values 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 reminds 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.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2000年第11期1345-1348,共4页
Acta Chimica Sinica
基金
高等学校博士学科点专项基金
关键词
电子对内相关
电子对间相关
HX体系
intrapair correlation of electrons, interpair correlation of electrons, HX(X=Li-F, HBe+ , HBe)
