Charge renormalization at the large-D limit for N-electron atoms and weakly bound systems

Kais, S.; Bleil, R.
May 1995
Journal of Chemical Physics;5/15/1995, Vol. 102 Issue 19, p7472
Academic Journal
We develop a systematic way to determine an effective nuclear charge ZRD such that the Hartree–Fock results will be significantly closer to the exact energies by utilizing the analytically known large-D limit energies. This method yields an expansion for the effective nuclear charge in powers of (1/D), which we have evaluated to the first order. This first order approximation to the desired effective nuclear charge has been applied to two-electron atoms with Z=2–20, and weakly bound systems such as H-. The errors for the two-electron atoms when compared with exact results were reduced from ∼0.2% for Z=2 to ∼0.002% for large Z. Although usual Hartree–Fock calculations for H- show this to be unstable, our results reduce the percent error of the Hartree–Fock energy from 7.6% to 1.86% and predicts the anion to be stable. For N-electron atoms (N=3–18, Z=3–28), using only the zeroth order approximation for the effective charge significantly reduces the error of Hartree–Fock calculations and recovers more than 80% of the correlation energy. © 1995 American Institute of Physics.


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