高等学校化学学报

高等学校化学学报 ›› 1994, Vol. 15 ›› Issue (6): 899.

• 论文 • 上一篇    下一篇

大基组在价键计算中的处理

莫亦荣, 吴玮, 张乾二   

  1. 厦门大学化学系, 厦门, 361005
  • 收稿日期:1993-07-01 出版日期:1994-06-24 发布日期:1994-06-24
  • 通讯作者: 莫亦荣,男,29岁,博士,讲师.
  • 作者简介:莫亦荣,男,29岁,博士,讲师.
  • 基金资助:

    国家自然科学基金;国家基础性研究重大关键项目

The Treatment of Big Basis Sets in Valence Bond Method

MO Yi-Rong, WU Wei, ZHANG Qian-Er   

  1. Department of Chemistry, Xiamen University, Xianien, 361005
  • Received:1993-07-01 Online:1994-06-24 Published:1994-06-24

PDF (PC)

被引次数

1

摘要： 编写了普适性的多键表自洽场程序,该程序能对单电子轨道展开系数和键表系数同时优化,其中单电子轨道的展开空间可任意定义,实际计算建议采用“杂化”轨道形式,即每个单电子轨道只对一个原子的基函数展开,对H2、Li2及HLi采用不同基组进行计算,结果表明用3个键表自洽计算所得能量与MP2结果相近,且我们的计算对键的共价性和离子性分析非常直观。

关键词: 价键理论, 自洽场, 杂化轨道

Abstract: Ageneralized multi-bonded tableau self-consistent field program(MBTSCF)is framed.The program can optimize the expansion coefficients of single-electron orbitals as well as those of bonded tableaus simultaneously.Though the expansion space of a singleelectron orbital can be defined arbitrarily, we suggest to adopt the form of a hybrid orbital whose expansion space is the basis functions of an unique atom.Test calculations to H2, Li2 and HLi are performed with different basis sets.The results show that the total energies resulted from 3BTSCF, where 3BT's correspond to resonance structures A-B, A+-B-and A--B+ for a diatomic molecule AB, are rather near to those resulted from MP2 calcula tions.Moreover, our method can be used to discuss the covalence and ionicity of a true molecular bond very intuitively.

Key words: Valence bond method, Self-consistent field, Hybrid orbital

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