Quantum Chemistry Close to the Fermi Level: Reducing Clusters to Few Active Hole and/or Electron Systems

Durand, Gérard; Spiegelman, Fernand

doi:10.1007/s00214-006-0100-x

Cited by 1 publication

(2 citation statements)

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“…Diatomics-in-molecule modeling of singly ionized rare gas clusters can also be expressed in a valence bond picture with a basis of atom-localized hole configurations and no internal geometrical structure. [58][59][60] That paved the way for extensive simulations of the electronic and dynamical properties of ionized rare gas clusters (see for instance Calvo et al 61,62 ).…”

Section: Introductionmentioning

confidence: 99%

“…An application to cationic molecular clusters of polycyclic aromatic hydrocarbon (PAH) was published by Bouvier et al, defining a resonance charge model based on frozen molecules and parametrized from ab initio CI calculations on dimers. Diatomics-in-molecule modeling of singly ionized rare gas clusters can also be expressed in a valence bond picture with a basis of atom-localized hole configurations and no internal geometrical structure. − That paved the way for extensive simulations of the electronic and dynamical properties of ionized rare gas clusters (see for instance Calvo et al , ).…”

Section: Introductionmentioning

confidence: 99%

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Modeling Charge Resonance in Cationic Molecular Clusters: Combining DFT-Tight Binding with Configuration Interaction

Rapacioli

Spiegelman

Scemama

et al. 2010

J. Chem. Theory Comput.

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In order to investigate charge resonance situations in molecular complexes, Wu et al. (J. Chem. Phys. 2007, 127, 164119) recently proposed a configuration interaction method with a valence bond-like multiconfigurational basis obtained from constrained DFT calculations. We adapt this method to the Self-Consistent Charge Density-Functional-based Tight Binding (SCC-DFTB) approach and provide expressions for the gradients of the energy with respect to the nuclear coordinates. It is shown that the method corrects the wrong SCC-DFTB behavior of the potential energy surface in the dissociation regions. This scheme is applied to determine the structural and stability properties of positively charged molecular dimers with full structural optimization, namely, the benzene dimer cation and the water dimer cation. The method yields binding energies in good agreement with experimental data and high-level reference calculations.

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