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Charge renormalization at the large‐ D limit for atoms and molecules
Author(s) -
Bleil Richard,
Kais Sabre
Publication year - 1995
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560560839
Subject(s) - homonuclear molecule , hartree–fock method , renormalization , hamiltonian (control theory) , heteronuclear molecule , effective nuclear charge , physics , charge (physics) , quantum mechanics , atomic physics , chemistry , molecule , ion , mathematical optimization , mathematics
By combining Hartree–Fock results for nonrelativistic ground‐state energies of atoms and molecules with analytic expressions for the large‐dimensional limit of atoms, we obtained a simple systematic renormalization procedure. This procedure is based on the variation of the nuclear charges, { Z i }, and internuclear distances, { R ij }, of the Hartree–Fock Hamiltonian such that the Hartree–Fock energy will be significantly closer to the exact energy. We calculate to first order in δZ the leading contribution to the correlation energy by changing the nuclear charge to some renormalized nuclear charge, Z + δ Z . Our goal is to find the parameter δ Z in a completely self‐consistent and systematic manner, which we accomplish by utilizing the analytically known solutions for both the exact and Hartree–Fock energies for all atoms in the large‐ D limit. We demonstrate that use of the dimensional renormalization parameter δ Z ∞ . Directly in standard Hartree–Fock calculations for atoms and homonuclear and heteronuclear molecules yields about 2/3 or more of the correlation energy. © 1995 John Wiley & Sons, Inc.