title: Correction for dispersion and Coulombic interactions in molecular clusters with density functional derived methods: application to polycyclic aromatic hydrocarbon clusters.
abstract: The density functional based tight binding (DFTB) is a semiempirical method derived from the density functional theory (DFT). It inherits therefore its problems in treating van der Waals clusters. A major error comes from dispersion forces, which are poorly described by commonly used DFT functionals, but which can be accounted for by an a posteriori treatment DFT-D. This correction is used for DFTB. The self-consistent charge (SCC) DFTB is built on Mulliken charges which are known to give a poor representation of Coulombic intermolecular potential. We propose to calculate this potential using the class IV/charge model 3 definition of atomic charges. The self-consistent calculation of these charges is introduced in the SCC procedure and corresponding nuclear forces are derived. Benzene dimer is then studied as a benchmark system with this corrected DFTB (c-DFTB-D) method, but also, for comparison, with the DFT-D. Both methods give similar results and are in agreement with references calculations (CCSD(T) and symmetry adapted perturbation theory) calculations. As a first application, pyrene dimer is studied with the c-DFTB-D and DFT-D methods. For coronene clusters, only the c-DFTB-D approach is used, which finds the sandwich configurations to be more stable than the T-shaped ones.
authors: Laboratoire de Chimie et Physique Quantiques, IRSAMC, Université de Toulouse, UPS and CNRS, 118 Route de Narbonne, F-31062 Toulouse, France. mathias.rapacioli@irsamc.ups-tlse.fr
authors: Mathias
authors: M
authors: Rapacioli
authors: Fernand
authors: F
authors: Spiegelman
authors: Dahbia
authors: D
authors: Talbi
authors: Tzonka
authors: T
authors: Mineva
authors: Annick
authors: A
authors: Goursot
authors: Thomas
authors: T
authors: Heine
authors: Gotthard
authors: G
authors: Seifert