Comparison of ring currents evaluated consistently at density functional and Hartree–Fock levels

Abstract

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.

Keywords:

• aromaticity
• DFT
• Hartree–Fock
• ring currents
• symmetry breaking

Acknowledgement

PWF thanks the Royal Society/Wolfson Scheme for financial support through a Research Merit Award. BJI thanks EPSRC for a DTA studentship.