Theoretical models incorporating electron correlation

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.…