Abstract
The shifted scheme of many-body perturbation theory is applied to open-shell states within the framework of the general-model-space theory. Rules for shifting the denominators of folded diagrams. which appear in open-shell perturbation expansions, are given. The finite-order energies in the shifted scheme obtained in two equivalent representations may differ. This happens, for instance, in the case of triplet states. For 3Σu + states of the He2, differences up to 0.07 mhartree have been found in third order. A similar phenomenon is the size inconsistency of the shifted scheme observed by Silver in the ground state of He2. A possible advantage of the shifted scheme is its faster convergence for excited states.
Original language | English |
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Pages (from-to) | 469-479 |
Number of pages | 11 |
Journal | Chemical Physics |
Volume | 62 |
Issue number | 3 |
DOIs | |
State | Published - 15 Nov 1981 |