American Institute of Physics, The Journal of Chemical Physics, 6(129), p. 064112
DOI: 10.1063/1.2938371
Full text: Unavailable
The present paper presents a revised version of a size-consistency correction to the multireference configuration interaction techniques previously proposed by Szalay et al. [J. Phys. Chem. 100, 6288 (1996)]. The method assumes a complete active space reference space and separates the nonreference determinants in several classes according to their number of inactive holes and particles. The correction is formulated as a dressing of the diagonal energies of these determinants, which depends on their class, as originally proposed by Ruttink et al. [J. Chem. Phys. 94, 7212 (1991)]. The exclusion principle violating corrections are evaluated through a simple counting of the various excitation processes which remain possible on each class. The efficiency of the method has been tested on a series of multireference problems for which full configuration interaction results are available (OH2 bond breaking, Be insertion in H2, excited states of CH2). The dressing of a given state not only provides excellent results for this state but also provides accurate excited roots. The efficiency of state-specific dressings is dramatic. The adaptation of this proposal to difference-dedicated configuration interactions can be extremely fruitful, as illustrated in the calculation of the 1Ag1-1Bu1(π−>π*) transition energy of the trans-butadiene molecule.