Size-consistent multireference configuration interaction method through the dressing of the norm of determinants

A new determinant-specific, effective change (‘dressing’) of the norm of the multireference configuration interaction (MRCI) wavefunction is proposed in order to achieve the size-consistency of the MRCI method. The new approach provides a unifying framework for analysis of size-consistent extensions of the MRCI method that are based on the coupled pair functional (CPF) strategy and lead to simplified computations of the analytical gradients. Using the new framework, a generalized multireference full coupled pair functional (MR-FCPF) method is introduced. The MR-FCPF method may be viewed as a functional counterpart of the recently proposed generalized (‘full’) coupled electron pair approximation (CEPA), referred to as the size-consistent self-consistent CI ((SC)²CI) method. A straightforward extension of the MR-FCPF method leads to a pseudo-functional form of the coupled cluster (CC) type formalisms. Therefore, the new approach may be used to introduce a simple alternative to existing CC-type gradient techniques. The new procedure is formally derived and compared with similar methods from the literature. Model systems calculations (H₂O, LiF, CH⁺ ₂) are further used to demonstrate the effect of various approximations and to elucidate the hierarchy of functional MR-CEPA schemes.