Restoring the size consistency of multireference configuration interactions through class dressings: applications to ground and excited states.
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 (OH(2) bond breaking, Be insertion in H(2), excited states of CH(2)). 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 1 (1)A(g)-1(1)B(u)(pi->pi(*)) transition energy of the trans-butadiene molecule.
Ben Amor
Nadia
N
Laboratoire de Chimie et Physique Quantiques, IRSAMC, Université Paul Sabatier, 118 de Narbonne, 31062 Toulouse Cedex, France. benamor@irsamc.ups-tlse.fr
Maynau
Daniel
D
Malrieu
Jean-Paul
JP
Monari
Antonio
A