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Extension of Coupled Cluster Methodology to Open Shells: State Universal Approach

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Recent Progress in Many-Body Theories

Abstract

A brief description of basic models and methods that are currently exploited in molecular electronic structure calculations indicates the desirability of extending the single-reference coupled-cluster (CC) approach to the multi-reference (MR) case. The recently developed explicit formalism of orthogonally spin-adapted, state-universal (or Hilbert space) MR-CC theory for the special case of closed-shell type references is applied to a simple four-electron model system formed by two interacting hydrogen molecules. Varying the geometry of the nuclear framework from the square configuration to a linear one this model simulates the breaking of a single chemical bond and enables a continuous transition to be made between the degenerate and non-degenerate regimes. The simplicity of the model enables a comparison with the exact solution, obtained by the full configuration interaction method. In this way the performance of the MR-CC approach at both linear and non-linear levels of approximation, nature and multiplicity of MR-CC solutions and the role played by the intruder states can be examined in considerable detail.

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Author notes

  1. P. Piecuch

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

Authors and Affiliations

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

    J. Paldus & P. Piecuch

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

    J. Paldus & L. Pylypow

  3. Department of Chemistry, University of Warsaw, Pasteura 1, 02-093, Warsaw, Poland

    B. Jeziorski

Authors
  1. J. Paldus
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  2. P. Piecuch
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  3. B. Jeziorski
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  4. L. Pylypow
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Editor information

Editors and Affiliations

  1. Texas A&M University College Station, Texas, USA

    T. L. Ainsworth , B. E. Clements  & E. Krotscheck ,  & 

  2. University of Minnesota Minneapolis, Minneapolis, Minnesota, USA

    C. E. Campbell

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Paldus, J., Piecuch, P., Jeziorski, B., Pylypow, L. (1992). Extension of Coupled Cluster Methodology to Open Shells: State Universal Approach. In: Ainsworth, T.L., Campbell, C.E., Clements, B.E., Krotscheck, E. (eds) Recent Progress in Many-Body Theories. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-3466-2_19

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  • DOI: https://doi.org/10.1007/978-1-4615-3466-2_19

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4613-6535-8

  • Online ISBN: 978-1-4615-3466-2

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