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Elsevier, Chemical Physics Letters, 4(241), p. 438-444

DOI: 10.1016/0009-2614(95)00650-s

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Degeneracy-corrected perturbation theory for electronic structure calculations

Journal article published in 1995 by Xavier Assfeld ORCID, Jan E. Almlöf, Donald G. Truhlar
This paper is available in a repository.
This paper is available in a repository.

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Abstract

The second-order perturbative treatment of molecular electronic energies is modified in a way that takes account of near-degeneracy effects. The resulting formalism (DCPT2) is just as easy to apply as the popular second-order Moller-Plesset theory (also called second-order many-body perturbation theory) but is more accurate because it is less sensitive to near-degeneracy effects. Illustrative calculations are reported for a series of small molecules, showing significant improvement for cases with lone pairs on vicinal atoms.