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Dimer centred basis set in the calculations of the first-order interaction energy with CI wavefunction

 

作者: Grzegorz Chałasiński,   Maciej Gutowski,  

 

期刊: Molecular Physics  (Taylor Available online 1985)
卷期: Volume 54, issue 5  

页码: 1173-1184

 

ISSN:0026-8976

 

年代: 1985

 

DOI:10.1080/00268978500100931

 

出版商: Taylor & Francis Group

 

数据来源: Taylor

 

摘要:

Assuming the monomer wavefunction in the form of a CI expansion in terms of orbitals of the whole dimer, the expression for the Heitler-London interaction energy is analyzed and implemented in the calculations of the He dimer. It is proved that the ‘zeroth-order exchange’ term Δ vanishes if the CI expansion is a full one. If the CI wavefunctions are complete up ton-fold excitations the contributions to Δ can be related only to excitations higher thann-fold ones. If the gaussian orbitals are used the problem of a gaussian asymptotic behaviour of the CI ansatz appears to be effectively circumvented.

 

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