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Size-consistent single-reference methods for electronic correlation: a unified formulation through intermediate hamiltonian theory

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Abstract

Using the intermediate hamiltonian theory as a unique conceptual frame and the technique of CI matrix dressing, a wide series of single-reference methods for the treatment of the ground state correlation are reviewed, compared, and sometimes improved. These methods range from independent excitation approximation (the very next step beyond MP2) to coupled cluster, going through the so-called electron pair approximations and the (SC)2CI formalism. A hierarchy of these methods can be established according to two criteria:

  1. 1.

    The physical effects incorporated in the model space, the choice of which is flexible.

  2. 2.

    The quality of the evaluation of the coefficients of the external space determinants. This evaluation, which remains based on a single reference expansion of the wave function, may simply ensure the size consistency or incorporate the linked contributions from the outer space.

These formulations in terms of diagonalizations of dressed CI matrices avoid convergence problems, but their main advantage is their flexibility, since they apply to multi-reference SDCI spaces as well as to SDCI spaces. The use of a common frame allows one to propose consistent combinations of methods of various costs for the treatment of various parts of the correlation energy.

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Authors and Affiliations

  1. Departament de Química Física, Facultat de Química, Universität de Valéncia, c/Dr. Moliner, 50, E-46100, Burjassot (Valencia), Spain

    José Sánchez-Marín & Ignacio Nebot-Gil

  2. Laboratoire de Physique Quantique, URA 505 du CNRS, Université Paul Sabatier, 118, Route de Narbonne, F-31062, Toulouse Cedex, France

    Jean Paul Malrieu, Jean Louis Heully & Daniel Maynau

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  1. José Sánchez-Marín
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  2. Ignacio Nebot-Gil
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  3. Jean Paul Malrieu
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  4. Jean Louis Heully
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  5. Daniel Maynau
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Sánchez-Marín, J., Nebot-Gil, I., Malrieu, J.P. et al. Size-consistent single-reference methods for electronic correlation: a unified formulation through intermediate hamiltonian theory. Theoret. Chim. Acta 95, 215–241 (1996). https://doi.org/10.1007/BF02335465

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  • DOI: https://doi.org/10.1007/BF02335465

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