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Regensburg 2013 – wissenschaftliches Programm

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O: Fachverband Oberflächenphysik

O 35: Poster Session I (Metal, semiconductor and oxide substrates: structure and adsorbates; Graphene)

O 35.54: Poster

Dienstag, 12. März 2013, 18:15–21:45, Poster B1

DFT+D Van-der-Waals C6 coefficients for ionic crystals — •Steffen Seiler and Bernd Meyer — Interdisziplinäres Zentrum für Molekulare Materialien und Computer-Chemie-Centrum, Universität Erlangen-Nürnberg

Previous studies have shown that Grimme’s dispersion correction to DFT [1] leads to an overestimation of the binding energy of molecules on ionic surfaces. The reason is that in the Grimme D2 scheme no distinction is made between Van-der-Waals C6 coefficients for neutral and charged species of the same element, although they clearly possess different polarizabilities. We propose a simple scheme for adjusting the C6 coefficients of the cations in ionic crystals which is based on the static polarizability. Thin films are exposed to an external electric field and the film polarizability is determined by linear regression of the induced dipole moment. The method has been applied to magnesium oxide and hydroxide and we obtained very similar C6 values for the Mg cations as recently proposed by the Grimme group based on TDDFT calculations [2]. To demonstrate the impact of the modified Van-der-Waals correction, calculated binding curves for the interaction of different small molecules (CH4, H2O and SiMe(OH)3) with magnesium oxide and hydroxide model clusters will be shown and the results will be compared to MP2 benchmark calculations.
[1] S. Grimme, J. Comp. Chem. 27, 1787 (2006).
[2] S. Ehrlich et al.,Chem. Phys. Chem. 12, 3414 (2011).

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