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Variational freedom in self-consistent field calculations with basis sets

 

作者: D.B. Cook,   P.W. Fowler,   B.T. Pickup,  

 

期刊: Molecular Physics  (Taylor Available online 1993)
卷期: Volume 80, issue 1  

页码: 213-218

 

ISSN:0026-8976

 

年代: 1993

 

DOI:10.1080/00268979300102201

 

出版商: Taylor & Francis Group

 

数据来源: Taylor

 

摘要:

In a closed-shell self-consistent field calculation on a molecule without symmetry the number of degrees of variational freedom is equal to the product of the dimensions of occupied and virtual spaces. It is shown that this relation also applies within each irreducible representation in the case where the molecule has symmetry, and that it can be generalized to open-shell and many-shell cases. Illustrative examples for large, highly symmetric molecules show that extensive variational freedom can persist even in minimal basis sets.

 

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