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Theoretical Chemistry Accounts

, Volume 124, Issue 5–6, pp 365–376 | Cite as

On finite basis set implementation of the exchange-only optimized effective potential method

  • Vitaly N. GlushkovEmail author
  • Sergiy I. Fesenko
  • Hariton M. Polatoglou
Regular Article

Abstract

In this paper, we analyze a structure of the basis set optimized effective potential (OEP) equations from the Fredholm alternative point of view and present one of possible numerical schemes to solve the OEP equation in a stable manner. The solution is constructed as a sum of a unique solution on the subspace of eigenfunctions of the response matrix with non-zero eigenvalues and a non-unique solution on a counterpart subspace with singular eigenvalues. Non-uniqueness of a solution is exploited to obtain a local effective potential that satisfies the condition for the highest occupied molecular orbital (HOMO) without restricting the variational freedom of the optimization procedure. Unlike the existing methods we implement the HOMO condition using the functions of the null-subspace. Numerical results for the total and orbital energies based on the proposed scheme are close to the corresponding literature data.

Keywords

Optimized effective potential Fredholm alternative Basis set optimization 

Notes

Acknowledgments

One of us (V.N.G.) would like to thank Prof. A.K. Theophilou and Prof. N. Gidopoulos for stimulating discussions during the early stages of this work.

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Copyright information

© Springer-Verlag 2009

Authors and Affiliations

  • Vitaly N. Glushkov
    • 1
    Email author
  • Sergiy I. Fesenko
    • 1
  • Hariton M. Polatoglou
    • 2
  1. 1.Department of Physics, Electronics and Computer SystemsNational University of DnepropetrovskDnepropetrovskUkraine
  2. 2.Department of PhysicsAristotle University of ThessalonikiThessalonikiGreece

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