Direct selected multireference configuration interaction calculations for large systems using localized orbitals

Nadia Ben Amor (1) , Fabienne Bessac (2, 1) , Sophie Hoyau (1) , Daniel Maynau (1)

1 GMO - Groupe THEO (LCPQ)
2 INP - PURPAN - Ecole d'Ingénieurs de Purpan

A selected multireference configuration interaction (CI) method and the corresponding code are presented. It is based on a procedure of localization that permits to obtain well localized occupied and virtual orbitals. Due to the local character of the electron correlation, using local orbitals allows one to neglect long range interactions. In a first step, three topological matrices are constructed, which determine whether two orbitals must be considered as interacting or not. Two of them concern the truncation of the determinant basis, one for occupied/virtual, the second one for dispersive interactions. The third one concerns the truncation of the list of two electron integrals. This approach permits a fine analysis of each kind of approximation and induces a huge reduction of the CI size and of the computational time. The procedure is tested on linear polyene aldehyde chains, dissociation potential energy curve, and reaction energy of a pesticide-Ca2+ complex and finally on transition energies of a large iron system presenting a light-induced excited spin-state trapping effect.

Domaines: Chimie théorique et/ou physique

Nadia Ben Amor, Fabienne Bessac, Sophie Hoyau, Daniel Maynau. Direct selected multireference configuration interaction calculations for large systems using localized orbitals. Journal of Chemical Physics, 2011, 135 (1), pp.014101/1-014101/14. ⟨10.1063/1.3600351⟩. ⟨hal-00870759⟩