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Energy extrapolation in CI calculations

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Abstract

A method of extrapolating the CI energy of large configuration subspaces is discussed and illustrated in a series of examples. Secular equations for selected groups of configurations are solved, while the influence of the remaining elements in the subspace is accounted for in a statistical manner. Criteria for judging the reliability of the extrapolation technique are developed and evidence is presented underscoring the need to go beyond the level of truncated CI calculations in obtaining excitation energy and potential surface results.

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References

  1. Schaefer,H.F.: The Electronic Structure of Atoms and Molecules, Addison-Wesley Co., Inc. 1972

  2. Roos,B.: Chem. Phys. Letters15, 153 (1972)

    Article  Google Scholar 

  3. Davidson,E.R., in: Proceedings of the first international congress in quantum chemistry (Menton 1973). Daudel,R., Pullman,B., Eds. Dordrecht: D. Reidel 1974

    Google Scholar 

  4. Pipano,A., Shavitt,I.: Intern. J. Quantum Chem.2, 741 (1968)

    Article  CAS  Google Scholar 

  5. Sinanoglu,O.: J. Chem. Phys.36, 706 (1962)

    Article  CAS  Google Scholar 

  6. Nesbet,R.K.: Phys. Rev.175, 2 (1968)

    Article  CAS  Google Scholar 

  7. Buenker,R.J., Peyerimhoff,S.D.: Theoret. Chim. Acta (Berl.)35, 33 (1974)

    Article  CAS  Google Scholar 

  8. Whitten,J.L., Hackmeyer,M.: J. Chem. Phys.51, 5584 (1969);

    Article  CAS  Google Scholar 

  9. Hackmeyer,M., Whitten,J.L.: J. Chem. Phys.54, 3739 (1971)

    Article  CAS  Google Scholar 

  10. Bender,C.F., Davidson,E.R.: Phys. Rev.183, 23 (1969); Langhoff,S.P., Elbert,S.T., Davidson,E.R.: to be published

    Article  CAS  Google Scholar 

  11. Gershgorn,Z., Shavitt,I.: Intern. J. Quantum Chem.2, 751 (1968)

    Article  CAS  Google Scholar 

  12. Buenker,R.J., Peyerimhoff,S.D.: Chem. Phys. Letters,29, 253 (1974)

    Article  CAS  Google Scholar 

  13. Buenker,R.J., Peyerimhoff,S.D.: Chem. Phys.8, 324 (1975)

    Article  CAS  Google Scholar 

  14. Buenker,R.J., Peyerimhoff,S.D.: Chem. Phys.8, 56 (1975)

    Article  CAS  Google Scholar 

  15. Elbert,S.T., Peyerimhoff,S.D., Buenker,R.J.: “All-valence-electron CI calculations on the electronic spectrum of Diborane” Chem. Phys., in press

  16. Vasudevan,K., Peyerimhoff,S.D., Buenker,J., Kammer,W.E.: Chem. Phys.7, 187 (1975)

    Article  CAS  Google Scholar 

  17. Buenker,R.J., Peyerimhoff,S.D.: Chem. Phys., in press

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Author notes

  1. Robert J. Buenker

    Present address: Department of Chemistry, University of Nebraska, 68508, Lincoln, Nebraska, USA

Authors and Affiliations

  1. Lehrstuhl für Theoretische Chemie, Universität Bonn, Germany

    Robert J. Buenker & Sigrid D. Peyerimhoff

Authors
  1. Robert J. Buenker
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  2. Sigrid D. Peyerimhoff
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Senior U.S. Scientist Awardee of the Alexander von Humboldt Foundation

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Buenker, R.J., Peyerimhoff, S.D. Energy extrapolation in CI calculations. Theoret. Chim. Acta 39, 217–228 (1975). https://doi.org/10.1007/BF00555301

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