On the Aromaticity of the Planar Hydrogen-Bonded (HF)3 Trimer.

Abstract

The nuclear magnetic shieldings and magnetically induced ring currents have been calculated for the planar ring-shaped hydrogen fluoride trimer (HF)3 at correlated ab initio and density functional theory levels. Calculations of the magnetically induced current densities using the gauge-including magnetically induced current (GIMIC) method show that, contrary to a recent suggestion, (HF)3 has, at the MP2/TZVPP level, a very small ring-current susceptibility of 0.37 nA/T. Thus, only a weak net current is passing across the H···F hydrogen bond. An external magnetic field perpendicular to the ring plane induces strong edge currents circling around each HF molecule giving rise to a nonvanishing magnetic shielding at the center of the ring. The GIMIC results are supported by calculations of the long-range magnetic shielding function; the long-range magnetic shielding is very small, indicating that the magnetically induced ring-current is very weak. The surprisingly large nucleus-independent chemical shift (NICS) value for (HF)3 was recently taken as an indication of "H-bonded aromaticity". The NICS value calculated at the CCSD/QZ2P level is 2.77 ppm. The present GIMIC and aromatic ring-current shielding study shows that some care has to be taken when using NICS values as aromaticity indices.