Behaviour of the XH-*-π and YX-*-π interactions (X, Y = F, Cl, Br and I) in the coronene π-system, as elucidated by QTAIM dual functional analysis with QC calculations. Issue 29 (3rd May 2018) - Hayashi, Satoko
Abstract : The XH-*-π(C24 H12 ) interactions appear on the outside ring of C24 H12, while YX-*-π(C24 H12 ) do both on the inside and outside rings. Abstract : The dynamic and static nature of XH-*-π and YX-*-π in the coronene π-system (π(C24 H12 )) is elucidated by QTAIM dual functional analysis, where * emphasizes the presence of bond critical points (BCPs) in the interactions. The nature of the interactions is elucidated by analysing the plots of the total electron energy densities H b ( r c ) versus H b ( r c ) − V b ( r c )/2 [=( ħ 2 /8 m )∇ 2 ρ b ( r c )] for the interactions at BCPs, where V b ( r c ) are the potential energy densities at the BCPs. The data for the perturbed structures around the fully optimized structures are employed for the plots in addition to those of the fully optimized structures. The plots are analysed using the polar coordinate of ( R, θ ) for the data of the fully optimized structures, while those containing the perturbed structures are analysed using ( θ p, κ p ), where θ p corresponds to the tangent line of each plot and κ p is the curvature. Whereas ( R, θ ) show the static nature, ( θ p, κ p ) represent the dynamic nature of the interactions. All interactions in X–H-*-π(C24 H12 ) (X = F, Cl, Br and I) and Y–X-*-π(C24 H12 ) (Y–X = F–F, Cl–Cl, Br–Br, I–I, F–Cl, F–Br and F–I) are classified by pure CS (closed shell) interactions and are characterized as having the vdW nature, except for X–H = F–H and Y–X = F–Cl, F–Br and F–I, which show the typical-HB nature without covalency. The structural features of the complexes are also discussed.