Atomic pseudopotentials for reproducing π-orbital electron behavior in sp 2 carbon atoms

Alexander Punter (1) , Paola Nava (1) , Yannick Carissan (1)

1 ISM2 - Institut des Sciences Moléculaires de Marseille

A pseudo-potential system for an sp 2 carbon atom is built and tested as a building block for various pseudo-hydrocarbon polyenes and polycyclic aromatic hydrocarbons. This pseudo-system has a central charge of Z = 1, it contains only one electron. It is employed in ab-initio calculations in which several physical characteristics including the orbital energies and first ionisation energy, as well as first excitation energy and UV spectra, are found to be well-reproduced by the pseudo-system. Remarkably, not only are the π excitation energies in good agreement with the reference calculations, but also transition densities and intensities, confirming that the virtual space obtained with the pseudo-potentials is of excellent quality. Finally, this approach is capable of reproducing the π electron systems of small or large, planar or near-planar hydrocarbons at low computational cost.

Keywords: Pseudo-potentials; sp 2 carbon; PAH; aromaticity; π system *

Domains: Chemical Sciences; Theoretical and/or physical chemistry

Alexander Punter, Paola Nava, Yannick Carissan. Atomic pseudopotentials for reproducing π-orbital electron behavior in sp 2 carbon atoms. International Journal of Quantum Chemistry, 2019, pp.e25914. ⟨10.1002/qua.25914⟩. ⟨hal-02048996⟩