ON THE DIFFERENT REPRESENTATIONS OF THE HOLE-CORRELATION FUNCTIONS IN THE HARTREE-FOCK AND THE HARTREE-FOCK-SLATER METHODS AND THEIR INFLUENCE ON BOND-ENERGY CALCULATIONS

被引:59
作者
TSCHINKE, V
ZIEGLER, T
机构
[1] Department of Chemistry, University of Calgary, Calgary, Alta. T2N 1N4
关键词
D O I
10.1063/1.459335
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We have investigated the change in shape of the Hartree-Fock Fermi-hole correlation function upon bond formation. Our analysis indicates that the molecular Fermi-hole correlation function is on the whole considerably more diffuse than its atomic counterpart. It is shown that this imbalance gives rise to HF bond energies which in many instances are much smaller than the experimental values. The imbalance is related to the so-called near degeneracy error, a well known feature of the HF method. It can be removed by introducing a limited configuration interaction calculation which ensures a proper dissociation limit as the bond is broken. The Fermi-hole correlation function adopted by the Hartree-Fock-Slater method does not introduce the same imbalance between molecular and atomic hole functions. The calculated bond energies are, as a consequence, much larger and in better agreement with experiment. It is suggested that the Hartree-Fock-Slater method in part introduces correlation by avoiding the near degeneracy error through a balanced description of the molecular and atomic hole functions. © 1990 American Institute of Physics.
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收藏
页码:8051 / 8060
页数:10
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