Theoretical Chemistry Accounts

, Volume 106, Issue 5, pp 339–351

Identification of deadwood in configuration spaces through general direct configuration interaction

Authors

  • Joseph Ivanic
    • Ames Laboratory USDOE and Department of Chemistry, Iowa State University, Ames, IA 50011, USA
  • Klaus Ruedenberg
    • Ames Laboratory USDOE and Department of Chemistry, Iowa State University, Ames, IA 50011, USA
Regular article

DOI: 10.1007/s002140100285

Cite this article as:
Ivanic, J. & Ruedenberg, K. Theor Chem Acc (2001) 106: 339. doi:10.1007/s002140100285

Abstract.

 In order to identify ineffective and, hence, superfluous configurations in algorithmically generated configuration spaces, a direct configuration interaction (CI) method has been developed for determining completely general configurational expansions based on arbitrary determinantal configuration lists. While based on the determinantal ordering scheme of Knowles and Handy, our direct CI algorithm differs from previous ones by the use of the Slater–Condon expressions in direct conjunction with single and double replacements. A full, as well as a completely general selected, CI program has been implemented. With it, full configuration spaces of Ne, C2, CO and H2O with up to about 40 million determinants have been investigated. It has been found that, in all cases, fewer than 1% of the configurations in a natural-orbital-based configuration expansion reproduce the exact results within chemical accuracy.

Key words: Configuration interaction – Direct full configuration interaction – Direct selected configuration interaction – Configuration interaction expansion truncation

Copyright information

© Springer-Verlag Berlin Heidelberg 2001