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Method of moments approach and coupled cluster theory

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Summary

The single reference coupled cluster (CC) approach to the many-electron correlation problem is examined from the viewpoint of the method of moments (MM). This yields generally an inconsistent (overcomplete) set of equations for cluster amplitudes, which can be solved either in the least squares sense or by selective projection process restricting the number of equations to that of the unknowns. These resulting generalized MM-CC equations always contain the standard CC equations as a special case. Since, in the MM-CC formalism, the Schrödinger equation will be approximately satisfied on a subspace spanned by non-canonical configurations, this procedure may be helpful in extending the standard single reference CC theory to quasi-degenerate situations. To examine the potential usefulness of this idea, we explore the linear version of the CC approach for systems with a quasi-degenerate reference, in which case the standard linear theory is plagued with singularities due to the intruder states. Implications of this analysis for the structure of the wavefunction are also briefly discussed.

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Author notes

  1. Piotr Piecuch

    Present address: Institue of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50-383, Wrocław, Poland

Authors and Affiliations

  1. Department of Applied Mathematics, University of Waterloo, N2L 3G1, Waterloo, Ontario, Canada

    Karol Jankowski, Josef Paldus & Piotr Piecuch

  2. Quantum Chemistry Group, Institute of Physics, Nicholas Copernicus University, ul. Grudziadzka 5, 87-100, Toruń, Poland

    Karol Jankowski

  3. Department of Chemistry and Guelph-Waterloo Center for Graduate Work in Chemistry, Waterloo Campus, University of Waterloo, N2L 3G1, Waterloo, Ontario, Canada

    Josef Paldus

Authors
  1. Karol Jankowski
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  2. Josef Paldus
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  3. Piotr Piecuch
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Killam Research Fellow 1987–89

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Jankowski, K., Paldus, J. & Piecuch, P. Method of moments approach and coupled cluster theory. Theoret. Chim. Acta 80, 223–243 (1991). https://doi.org/10.1007/BF01117411

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  • DOI: https://doi.org/10.1007/BF01117411

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