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Dresden 2017 – scientific programme

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MM: Fachverband Metall- und Materialphysik

MM 35: Electronic Structure Theory: New Concepts and Developments in Density Functional Theory and Beyond

MM 35.7: Poster

Tuesday, March 21, 2017, 18:30–20:30, P2-OG4

Deciphering chemical bonding with Fermi-Löwdin orbitals — •Torsten Hahn1, Sebastian Schwalbe1, Jens Kortus1, and Mark Pederson21Institute for Theoretical Physics, TU Freiberg, Germany — 2Department of Chemistry, Johns Hopkins University, Baltimore Maryland (MD), US

The recently developed Fermi-Löwdin orbital based method for the correction of the self-interaction error within Density Functional Theory (FLO-SIC) [1,2] does provide improved orbital eigenvalues and more realistic level ordering [3]. We demonstrate the versatility of this method to provide details of chemical bonding by applying it to several systems featuring both localized and delocalized multi-center chemical bonding.

We present results on systems with varying structural complexity: Boron clusters, compounds containing planar tetra-coordinated carbon as well as several aromatic and anti-aromatic molecules. The FLO-SIC method yields an inherently ‘chemical’ representation of bonding in terms of Lewis-type lone and binding electron pairs as well as delocalized multi-center, many-electron bonds. We anticipate that this parameter free methodology becomes a reliable tool to obtain insights into fundamental bonding details especially in situations where standard DFT fails.

[1] M. R. Pederson et.al, JCP 140, 121103 (2014).

[2] M. R. Pederson, JCP 142, 064112 (2015).

[3] T. Hahn et al., JCP 143, 224104 (2015).

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