组态相互作用中的特征波函数

Abstract

提出了完全活性空间组态相互作用方法中对称化算符、本征基、特征矩阵、特征波函数等概念和将多电子波函救按空间与自旋对称分类的统一方法。按此法对称化算符并作用在特征波函数上，再按等价权空间求和即得全组态波函数。因对称性使组态函数中物理因子与几何因子完全分离，可消除了变分求解中多余的变量。特征基化学概念明确，直接对应给定的价键结构。

The multi-electron conFigurational Functions in complete active space (CAS) are classiFied and characterized by weight vectors (occupation numbers of orbitals).Each conFiguration has a given weight vector.ConFiguration space invariant under molecular point group is called equivalent weight space.The Slater determinants are basis Functions in each equivalent weight space.The new concepts of symmetrization operators,character Slater bases, character matrices and character conFiguration Functions, and general generation methods of symmetrization Function (eigenFunction of S2 and irreducible representation of molecular point group) are proposed.According to this scheme,the Full conFigurational Functions are a sum of these Functions obtained by operating the symmetrization operator to character conFiguration Functions, thereFore, the physical Factors and geometric Factors in Full conFiguration Functions are completely separated and redundant variance parameters are removed due to symmetry adaptation.The character Slater bases are one-one correspondence with equivalent VB structure and have a deFine chemical signiFicance.This method might play an important role in the CI theory and calculations.