Journal of Physical Chemistry A, Vol.117, No.8, 1804-1816, 2013
Dynamic Behavior of Hydrogen Bonds from Pure Closed Shell to Shared Shell Interaction Regions Elucidated by AIM Dual Functional Analysis
The dynamic behavior of hydrogen bonds (HBs) was clarified for the wide range of interactions applying AIM dual functional analysis. Plots of H-b(r(c)) versus H-b(r(c)) - V-b(r(c))/2 are analyzed in the polar (R, theta) representation, where H-b(r(c)) and V-b(r(c)) are total electron and potential energy densities at bond critical points, respectively, for the fully optimized structures Data of the fully optimized structure and four perturbed ones around it are plotted for each interaction, which give a specific curve. The curve is analyzed by (theta(p), kappa(p)): theta(p) corresponds to the tangent line from the y-direction and kappa(p) is the curvature. -Whereas (R, theta) correspond to the static nature, (theta(p), kappa(p)) represent the dynamic nature of interactions. Indeed, HBs can be classified only by one parameter of theta, but theta(p) supplies more information necessary for better understanding of HBs. Although H2Se-*-HSeH and H3N-*-HNH2 show the nature of pure CS (closed shell) of the vdW-type, H2S-*-HSH and H2O-*-HOH contain the nature of pure CS other than the vdW-type (HB-typical). The regular CS nature is observed for B-*-HF = HF, H2Se, H2S, H2O, and H92C=-0). The HF-*HF interaction is described as HB-typical, whereas others are by CTmc-type. The nature of H3N-*-HX (X = F, Cl, Br) is regular CS of the CTTBp-type. HBs in charged species, such as [HOH-*-OH](-) and [H2O-*-H-*-OH2](+), show the weak covalent nature of SS (shard us to understand HBs in more detail, in addition to the static behavior. shell). The dynamic behavior of HBs helps