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Article Dans Une Revue Journal of Chemical Physics Année : 2008

Restoring the size consistency of multireference configuration interactions through class dressings: Applications to ground and excited states

Nadia Ben Amor
Daniel Maynau
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Jean-Paul Malrieu
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Antonio Monari

Résumé

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 (OH2bond 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.
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Dates et versions

hal-00951057 , version 1 (24-02-2014)

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Nadia Ben Amor, Daniel Maynau, Jean-Paul Malrieu, Antonio Monari. Restoring the size consistency of multireference configuration interactions through class dressings: Applications to ground and excited states. Journal of Chemical Physics, 2008, 129, pp.064112. ⟨10.1063/1.2938371⟩. ⟨hal-00951057⟩
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