Halogen bonding: An AIM analysis of the weak interactions

A series of complexes formed between halogen-containing molecules and ammonia have been investigated by means of the atoms in molecules (AIM) approach to gain a deeper insight into halogen bonding. The existence of the halogen bond critical points (XBCP) and the values of the electron density (rho(b)) and Laplacian of electron density (del(2)rho(b)) at the XBCP reveal the closed-shell interactions in these complexes. Integrated atomic properties such as charge, energy, polarization moment, volume of the halogen bond donor atoms, and the corresponding changes (Delta) upon complexation have been calculated. The present calculations have demonstrated that the halogen bond represents different AIM properties as compared to the well-documented hydrogen bond. Both the electron density and the Laplacian of electron density at the XBCP have been shown to correlate well with the interaction energy, which indicates that the topological parameters at the XBCP can be treated as a good measure of the halogen bond strength. In addition, an excellent linear relationship between the interatomic distance d(X center dot center dot center dot N) and the logarithm of rho(b) has been established.