Green’s functions in quantum chemistry I. The Σ perturbation method

As an improvement over the Hartree-Fock approximation, we investigate a Green’s Function method—theΣ perturbation method—for molecular calculations. The method is applied to hydrogen molecule and to theπ-electron system of ethylene under PPP approximation. When the algebraic approximation is used, the energy obtained is better than that of the HF approach, but is not as good as that of the configuration-interaction method. The main advantage of this procedure is that it is devoid of the most serious defect of HF method, viz. incorrect dissociation limits.