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New perspectives in multireference perturbation theory: the n-electron valence state approach

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Abstract

The n-electron valence state perturbation theory (NEVPT) is a form of multireference perturbation theory which is based on a zero order reference wavefunction of CAS-CI type (complete active space configuration interaction) and which is characterized by the utilization of correction functions (zero order wavefunctions external to the CAS) of multireference nature, obtained through the diagonalization of a suitable two-electron model Hamiltonian (Dyall’s Hamiltonian) in some well defined determinant spaces. A review of the NEVPT approach is presented, starting from the original second order state-specific formulation, going through the quasidegenerate multi-state extension and arriving at the recent implementations of the third order in the energy and of the internally contracted configuration interaction. The chief properties of NEVPT—size consistence and absence of intruder states—are analyzed. Finally, an application concerning the calculation of the vertical spectrum of the biologically important free base porphin molecule, is presented.

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Authors and Affiliations

  1. Dipartimento di Chimica, Università di Ferrara, Via Borsari 46, 44100, Ferrara, Italy

    Celestino Angeli, Mariachiara Pastore & Renzo Cimiraglia

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  1. Celestino Angeli
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  2. Mariachiara Pastore
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  3. Renzo Cimiraglia
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Correspondence to Renzo Cimiraglia.

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Angeli, C., Pastore, M. & Cimiraglia, R. New perspectives in multireference perturbation theory: the n-electron valence state approach. Theor Chem Account 117, 743–754 (2007). https://doi.org/10.1007/s00214-006-0207-0

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  • DOI: https://doi.org/10.1007/s00214-006-0207-0

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