Acta Chimica Sinica ›› 1997, Vol. 55 ›› Issue (1): 1-8.     Next Articles

Original Articles

密度泛函理论与Hartree-Fock方法混合处理中的稳态相关能校正

杨晓梅;吴国是   

  1. 清华大学化学系
  • 出版日期:1997-01-15 发布日期:1997-01-15

Stationary correlation energy in the hybrid approach of density functional theory and Hartree-Fock method

YANG XIAOMEI;WU GUOSHI   

  • Online:1997-01-15 Published:1997-01-15

The equivalence condition of the correlation energy definition in Hartree-Fock method (HF) and in Density Functional Theory (DFT) is analyzed. It is shown that when the reference electron density is far from the actual density of the system concerned, two definitions don't give the same values and the DFT correlation energy is larger than the HF one in magnitude. Meanwhile, the correlation energy calculated by the hybrid approach of DFT and HF is smaller than the HF value in magnitude, the difference being explained by the stationary correlation energy. It is also verified that the difference can be estimated by limited CI method with appropriate configurations. The potential curves of several diatomic molecules H2 (X^1∑g^+), HF (X^1∑^+), N2 (^1∑g^+) are computed, all are better than those by CISD or MP4 method. Furthermore, the calculated dissociation energy of H2 is 0.17a. u., in agreement with the experimental value, 0.1747 a. u..

Key words: CONFIGURATION

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