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Journal of Chemical Physics / Volume 124 / Issue 20 / ARTICLES / Theoretical Methods and Algorithms

J. Chem. Phys. 124, 204109 (2006); http://dx.doi.org/10.1063/1.2204601 (6 pages)

Bounds on the overlap of the Hartree-Fock, optimized effective potential, and density functional approximations with the exact energy eigenstates

S. Thanos and A. K. Theophilou

Institute of Materials Science, DEMOCRITOS NCSR, TT 15310 Athens, Greece

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(Received 20 March 2006; accepted 19 April 2006; published online 25 May 2006)

In this paper, we examine the limits of accuracy of the single determinant approximations (Hartree-Fock, optimized effective potential, and density functional theory) to the exact energy eigenstates of many electron systems. We show that an approximate Slater determinant of Sz = M gives maximum accuracy for states with S = M, provided that perturbation theory for the spin up minus spin down potential is applicable. The overlap with the exact energy eigenstates with S ≠ M is much smaller. Therefore, for the case that the emphasis is on wave functions, one must use symmetry preserving theories, although this is at the expense of accuracy in energy.

© 2006 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. EXPANSION OF A SLADET IN TERMS OF EIGENSTATES OF S2
  3. CONCLUSIONS

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KEYWORDS and PACS

Keywords

HF calculations, density functional theory, perturbation theory, wave functions

PACS

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.2204601

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

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$abstract.society.value is a Member of CrossRef American Institute of Physics

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