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Theoretical models incorporating electron correlation
Author(s) -
Pople John A.,
Binkley J. Stephen,
Seeger Rolf
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560100802
Subject(s) - electronic correlation , gaussian , statistical physics , perturbation theory (quantum mechanics) , electron , møller–plesset perturbation theory , consistency (knowledge bases) , quantum mechanics , third order , physics , dissociation (chemistry) , chemistry , computational chemistry , mathematics , geometry , philosophy , theology
Some methods of describing electron correlation are compared from the point of view of requirements for theoretical chemical models. The perturbation approach originally introduced by Møller and Plesset, terminated at finite order, is found to satisfy most of these requirements. It is size consistent, that is, applicable to an ensemble of isolated systems in an additive manner. On the other hand, it does not provide an upper bound for the electronic energy. The independent electron‐pair approximation is accurate to second order in a Møller‐Plesset expansion, but inaccurate in third order. A series of variational methods is discussed which gives upper bounds for the energy, but which lacks size consistency. Finally, calculations on some small molecules using a moderately large Gaussian basis are presented to illustrate these points. Equilibrium geometries, dissociation energies, and energy separations between electronic states of different spin multiplicities are described substantially better by Moller‐Plesset theory to second or third order than by Hartree‐Fock theory.