Relativistic effects on the aromaticity of the halogenated benzenes: C6X6, X = H, F, Cl, Br, I, At.

ABSTRACT

In this study we report about the relativistic effects on the aromaticity of the six hexahalogenated compounds (C6H6, C6F6, C6Cl6, C6Br6, C6I6 and C6At6), via a magnetically induced current density method. All-electron density functional theory (DFT) calculations were carried out using the four-component Dirac-Coulomb (DC) Hamiltonian, including scalar and spin-orbit (SO) relativistic effects. Fully relativistic values of the magnetically induced ring currents were obtained by numerical integration over the current flow. These values were compared to the spin-free (SO interaction switched off) and non-relativistic values, in order to assess the corresponding contributions to aromaticity. It was found that in C6I6 and C6At6 there is a strong SO influence, in line with the expected relativistic effects of the heavy elements, iodine and astatine.