| Abstract
| - This work proposes a simple yet accurate methodology to account for charge resonance in ionic clusters. Thesupersystem's model Hamiltonian is described via a basis set of valence bond structures for which the chargeis localized on a given monomer, and whose intermolecular binding energies are computed using a polarizablemodel potential. The coupling elements between these structures are proportional to an overlap integral betweenrelevant nonorthogonal monomer molecular orbitals. Ab initio calculations are employed to calibrate andvalidate the model, but also to define its limits. The methodology is then applied to the global exploration ofpotential energy surfaces for small homocluster ions of benzene, naphthalene, and anthracene. The structuraland electronic properties of these systems are discussed, with emphasis on important trends such as thepolarization vs charge-transfer competition or the difference between adiabatic and vertical ionization potentials.Extensions to stacked cluster ions of higher aggregation number (n = 15) conclude this work.
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