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Modified Perturbation Theory for Atoms and Molecules Based on a Hartree–Fock φ (in ZZ)

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.1670363· OSTI ID:4479752
 [1];  [1]
  1. Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland
+ Show Author Affiliations
The improvement of Hartree–Fock wavefunctions by perturbation theory is hampered by slow convergence with the usual choice of H0 =  ∑ i = 1N F(i), where F denotes the one-electron Hartree–Fock Hamiltonian. The slow convergence is usually attributed to the unphysical nature of the excited states of F, which do not describe electrons moving in the field of the nuclei, shielded by N-1 electrons. It is shown how to redefine F so that the zeroth-order wavefunction still remains the Hartree–Fock wavefunction but so that the excited states of F correspond to an electron moving in the field of the nuclei screened by N-1 electrons. The redefined F thus results in a more appropriate H0. Calculations of some second-order polarization and semi-internal correlation energies in first-row atoms are given to illustrate the use of the redefined F.
Research Organization:
Originating Research Org. not identified
NSA Number:
NSA-22-050018
OSTI ID:
4479752
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 5 Vol. 49; ISSN 0021-9606
Country of Publication:
Country unknown/Code not available
Language:
ZZ

References (15)

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