Ab-initio multireference study of an organic mixed-valence Spiro molecular system. - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Computational Chemistry Année : 2009

Ab-initio multireference study of an organic mixed-valence Spiro molecular system.

Wissam Helal
  • Fonction : Auteur
Stefano Evangelisti
Thierry Leininger
Daniel Maynau
  • Fonction : Auteur

Résumé

The electronic structure and some electron transfer properties of a model mixed-valence Spiro molecular cation have been investigated at CAS-SCF, CAS+S, and CAS+SD levels starting from canonical and localized orbitals, using SZ, DZ, and TZP basis sets. The potential energy surfaces of the adiabatic ground and the lowest three excited electronic states have been computed, within a two-state model, and a double-well potential has been obtained for the ground electronic state. We have demonstrated the low coupling interaction between the two redox moieties of this molecular cation by following the charge localization/delocalization in the valence pi system through the reaction coordinate of the intramolecular charge transfer. The effect of dynamical correlation, using either localized or canonical orbitals, was found to be crucial for a quantitative description of the electronic structure and some important electron transfer parameters of this mixed-valence system.

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Dates et versions

hal-00871241 , version 1 (09-10-2013)

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Wissam Helal, Stefano Evangelisti, Thierry Leininger, Daniel Maynau. Ab-initio multireference study of an organic mixed-valence Spiro molecular system.. Journal of Computational Chemistry, 2009, 30 (1), pp.83-92. ⟨10.1002/jcc.20982⟩. ⟨hal-00871241⟩
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