Theoretica chimica acta

, Volume 84, Issue 1–2, pp 95–103

Internally contracted multiconfiguration-reference configuration interaction calculations for excited states

  • Peter J. Knowles
  • Hans-Joachim Werner

DOI: 10.1007/BF01117405

Cite this article as:
Knowles, P.J. & Werner, HJ. Theoret. Chim. Acta (1992) 84: 95. doi:10.1007/BF01117405


The calculation of electronically excited states with the internally contracted multiconfiguration-reference configuration interaction (CMRCI) method is discussed. A straightforward method, in which contracted functions for all states are included in the basis, is shown to be very accurate and stable even in cases of narrow avoided crossings. However, the expense strongly increases with the number of states. A new method is proposed, which employs different contracted basis sets for each state, and in which eigensolutions of the Hamiltonian are found using an approximate projection operator technique. The computational effort for this method scales only linearly with the number of states. The two methods are compared for various applications.

Key words

Quantum chemistry Configuration interaction Excited states 

Copyright information

© Springer-Verlag 1992

Authors and Affiliations

  • Peter J. Knowles
    • 1
  • Hans-Joachim Werner
    • 2
  1. 1.School of Chemistry and Molecular SciencesUniversity of SussexFalmer, BrightonUK
  2. 2.Fakultät für ChemieUniversität BielefeldBielefeldFederal Republic of Germany

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