Comparison of ring currents evaluated consistently at Density Functional and Hartree-Fock levels

Remco Havenith (1) , Anthony Meijer (2) , Benjamin Irving (2) , Patrick Fowler (2)

1 Theoretical Chemistry
2 Department of Chemistry [Sheffield]

Ring-current maps give an immediate visualisation of aromaticity on the magnetic criterion - by which a cyclic system that supports diatropic (paratropic) current induced by a perpendicular magnetic field is aromatic (anti-aromatic). Calculations of maps with the ipsocentric choice of origin are made in the 6-31G** basis set at Hartree Fock (HF) and Density Functional (DFT) levels (PW91 and B3LYP functionals) on porphyrin, porphycene, orangarin, sapphyrin and hexabenzocoronene. In these systems, DFT and HF approaches produce optimal geometries with different point-group symmetries and/or different patterns of bond alternation. The ring-current maps derived with all four combinations of methods indicate that the main features of the current (global nature, direction, estimated strength) survive in systems with symmetry-breaking, but that choice of geometry is more critical for the detail of the current than is the electronic-structure method.

Mots clés: Physical Sciences

Remco Havenith, Anthony Meijer, Benjamin Irving, Patrick Fowler. Comparison of ring currents evaluated consistently at Density Functional and Hartree-Fock levels. Molecular Physics, 2009, 107 (23-24), pp.2591-2600. ⟨10.1080/00268970903449396⟩. ⟨hal-00548166⟩