ISSN:
0020-7608
Keywords:
Chemistry
;
Theoretical, Physical and Computational Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
It has been known since the work of March and White that the simplest nonrelativistic density functional theory, namely, the statistical method of Thomas, Fermi, and Dirac, sums subseries of the so-called 1/Z expansion to yield, for heavy neutral atoms, the ground-state energy E= - a0Z7/3+ a1Z2-a2Z5/3+⋅⋅⋅. The term of O(Z5/3) is the Dirac-Slater exchange energy Eexc, and it is of considerable interest to know at what order the correlation energy Ecorr enters this expansion. Dimensional scaling considerations by Kais et al. suggested Ecorr∝Z4/3 in the limit of large Z. Here, attention is focused on whether this can be distinguished empirically from a term of the form (aZ ln Z+bZ) for neutral atoms. If the latter term is correct, then a relationship between Ecorr and the Shannon information entropy can be forged analytically for large atomic number Z in nonrelativistic theory. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 721-726 (1998)
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
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