ISSN:
0020-7608
Schlagwort(e):
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
By combining Hartree-Fock results for nonrelativistic ground-state energies of N-electron atoms with analytic expressions for the large-dimension limit, we have obtained a simple renormalization procedure. For neutral atoms, this yields energies typically threefold more accurate than the Hartree-Fock approximation. Here, we examine the dependence on Z and N of the renormalized energies E(N, Z) for atoms and cations over the range Z, N = 2 → 290. We find that this gives for large Z = N an expansion of the same form as the Thomas-Fermi statistical model, E → Z7/2(C0 + C1Z-1/3 + C2Z-2/3 + C3Z-3/3 + ⃛), with similar values of the coefficients for the three leading terms. Use of the renormalized large-D limit enables us to derive three further terms. This provides an analogous expansion for the correlation energy of the form δE δZ4/3(δC3 + δC5Z-2/3 + δC6Z-3/3 + ⃛); comparison with accurate values of δE available for the range Z ≤ 36 indicates the mean error is only about 10%. Oscillatory terms in E and δE are also evaluated. © 1994 John Wiley & Sons, Inc.
Zusätzliches Material:
6 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/qua.560490511
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