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The role of orbital transformations in coupled-pair functionals

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Abstract

The replacement of single excitations by orbital transformations in coupled-pair functionals derived from a single double configuration interaction approach is discussed. It is demonstrated that this modification leads to considerably improved density matrices and better agreement with results from coupled cluster singles doubles calculations taken as a reference. A comparison between the variationally optimized orbitals and the Brueckner orbitals shows that these two sets of orbitals are different.

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Acknowledgment

C. K. would like to thank F. Neese and H.-J. Werner for stimulating discussions.

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Authors and Affiliations

  1. Lehrstuhl für Theoretische Chemie, Universität Bonn, Wegelerstr. 12, 53115, Bonn, Germany

    Christian Kollmar

  2. Lehrstuhl für Theoretische Chemie, Universität Erlangen, Egerlandstraße 3, 91058, Erlangen, Germany

    Andreas Heßelmann

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  1. Christian Kollmar
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  2. Andreas Heßelmann
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Correspondence to Christian Kollmar.

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Kollmar, C., Heßelmann, A. The role of orbital transformations in coupled-pair functionals. Theor Chem Acc 127, 311–325 (2010). https://doi.org/10.1007/s00214-009-0719-5

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